Low volatility auxin herbicide formulations

ABSTRACT

Low volatility dicamba herbicide formulations are described. In some embodiments, concentrate formulations comprising dicamba monoethanolamine salt, dicamba potassium salt, or mixed dicamba salts are provided. In other embodiments, a dicamba salt is combined with a polybasic polymer.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 13/389,864, filed Feb. 10, 2012, based on PCT applicationPCT/US10/44873, filed Aug. 9, 2010, claiming priority to U.S.Provisional Application No. 61/232,710, filed Aug. 10, 2009, the entiredisclosures of which are incorporated by reference.

FIELD OF THE INVENTION

The present invention generally relates to low volatility auxinherbicide formulations.

BACKGROUND OF THE INVENTION

Auxin herbicides have proven to be effective and highly beneficial forcontrol of unwanted plants. Auxin herbicides include 2,4-D(2,4-dichlorophenoxyacetic acid), 2,4-DB(4-(2,4-dichlorophenoxy)butanoic acid), dichloroprop(2-(2,4-dichlorophenoxy)propanoic acid), MCPA((4-chloro-2-methylphenoxy)acetic acid), MCPB(4-(4-chloro-2-methylphenoxy)butanoic acid), am inopyralid(4-amino-3,6-dichloro-2-pyridinecarboxylic acid), clopyralid(3,6-dichloro-2-pyridinecarboxylic acid), fluroxypyr([(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid), triclopyr([(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid), diclopyr, mecoprop(2-(4-chloro-2-methylphenoxy)propanoic acid) and mecoprop-P, dicamba(3,6-dichloro-2-methoxybenzoic acid), picloram(4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid), quinclorac(3,7-dichloro-8-quinolinecarboxylic acid), am inocyclopyrachlor(6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid),agriculturally acceptable salts of any of these herbicides, racemicmixtures and resolved isomers thereof, and mixtures thereof. Dicamba hasproven to be a particularly effective auxin herbicide and is typicallyformulated as the sodium, dimethylamine, isopropylamine or diglycolaminesalt.

Volatility and drift problems are commonly associated with auxinherbicides. Volatile auxin herbicides can, under certain conditions ofapplication, vaporize into the surrounding atmosphere and therebymigrate from the application site to adjacent crop plants, such assoybeans and cotton, where contact damage to sensitive plants can occur.Spray drift can be attributed to volatility as well as to the physicalmovement of small particles, such as spray droplet particles, from thetarget site to adjacent crop plants.

Prior art solutions to volatility and drift have failed to successfullyregulate off-target dicamba movement from the application site. Attemptsto reduce volatility have been made by formulating dicamba in the formof various mineral or amine salts. For example, the commercial productCLARITY® (available from BASF) is a formulation comprising thediglycolamine salt of dicamba and the commercial product BANVEL®(available from BASF) is a formulation comprising the dimethylamine saltof dicamba. Problematically however, crop plants such as soybean andcotton or sensitive plants such as vegetables and flowers located in anarea wherein CLARITY or BANVEL has been applied can still exhibitsymptoms of injury such as leaf cupping, leaf malformation, leafnecrosis, terminal bud kill and/or delayed maturity.

Other attempts to reduce dicamba volatilization have focused onencapsulation. In one approach, dicamba is absorbed into solid phasenatural or synthetic polymers. However, the resulting particle sizes aretypically not suitable for spray application therefore limiting use togranular drop application. Microencapsulation in a polymer shell is alsoknown in the art, but the relatively high solubility of dicamba and itssalts precludes successful use of that technology in aqueous suspensionsand commercial dicamba microencapsulation products have not beendeveloped.

A need persists for low volatility auxin herbicide formulations that areefficacious, yet non-phytotoxic to sensitive crops located in areasadjacent to the target site, and for auxin formulations that are lessprone to volatility and physical drift.

SUMMARY OF THE INVENTION

Among the various aspects of the present invention may be noted theprovision of auxin herbicide formulations exhibiting low volatilityand/or drift and methods for their use.

Briefly, therefore, the present invention is directed to an aqueousherbicidal solution concentrate formulation useful for killing orcontrolling the growth of unwanted plants, the formulation comprising asolution comprising an auxin herbicide component consisting essentiallyof auxin herbicide salts and comprising at least 50 grams acidequivalent per liter of dicamba monoethanolamine salt.

The present invention is further directed to an aqueous herbicidalsolution concentrate formulation useful for killing or controlling thegrowth of unwanted plants, the formulation comprising a solutioncomprising an auxin herbicide component consisting essentially of auxinherbicide salts and comprising at least 550 grams acid equivalent perliter of dicamba potassium salt.

The present invention is further directed to an aqueous herbicidalsolution concentrate formulation useful for killing or controlling thegrowth of unwanted plants, the formulation comprising an auxin herbicidecomponent consisting essentially of auxin herbicide salts and comprisingat least 50 grams acid equivalent per liter of dicamba diethanolaminesalt.

The present invention is further directed to low volatility auxinherbicide formulations comprising an auxin herbicide componentconsisting essentially of an auxin herbicide salt or a mixture of auxinherbicide salts and a polybasic polymer or mixture of polybasicpolymers, wherein the formulation is an aqueous solution. The polymerhas a molecular weight of from 600 to 3,000,000 Daltons and has anitrogen content of from 13 to 50 percent by weight

The present invention is further directed to a method of using an auxinherbicide to control auxin-susceptible plants growing in and/or adjacentto a field of crop plants. The method comprises diluting a formulationcomprising a solution of (i) at least 50 grams acid equivalent per literof dicamba monoethanolamine salt or dicamba diethanolamine salt or atleast 550 grams acid equivalent per liter of dicamba potassium salt withwater to provide an aqueous herbicidal application mixture or (ii)forming an aqueous application mixture from a low volatility auxinherbicide formulation comprising an auxin herbicide component consistingessentially of an auxin herbicide salt or a mixture of auxin herbicidesalts and a polybasic polymer or mixture of polybasic polymers. Theaqueous herbicidal application mixture is applied to the foliage of theauxin-susceptible plants.

The present invention is further directed to a method of reducing thevolatility of auxin herbicides. The method comprises providing anitrogen containing polybasic polymer source for use in preparation ofan aqueous herbicidal application mixture comprising an auxin herbicidefor application to auxin susceptible plants. The auxin herbicide contentof said auxin herbicide consists essentially of the salts of one or moreauxin herbicide species. The polybasic polymer has a molecular weightfrom 600 to 3,000,000 Daltons and has a nitrogen content from 10 to 50percent by weight.

The present invention is still further directed to a method forcontrolling auxin susceptible plants. The method comprises obtaining anitrogen containing polybasic polymer source comprising at least onepolybasic polymer species, wherein the polybasic polymer has an averagemolecular weight of from 600 to 3,000,000 Daltons and has an averagenitrogen content of from 13 to 50 percent by weight and obtaining anauxin herbicide source having a herbicide content consisting essentiallyof one or more auxin herbicide salt species. The nitrogen containingpolybasic polymer source and auxin herbicide source are mixed with waterto produce an aqueous auxin application mixture that is applied to theauxin susceptible plants.

The present invention is yet further directed to a method of counselinga person responsible for control of auxin susceptible plants. The methodcomprises (i) identifying an auxin herbicide source to be used in thepreparation of an aqueous auxin application mixture, the auxinherbicides contained in said auxin herbicide source consistingessentially of one or more auxin herbicide salt species, (ii)identifying a nitrogen containing polybasic polymer source comprising atleast one polybasic polymer species, wherein the polybasic polymer hasan average molecular weight of from 600 to 3,000,000 Daltons and has anaverage nitrogen content of from 13 to 50 percent by weight and (iii)enabling said person to prepare said aqueous auxin application mixturefrom materials comprising said auxin herbicide source and said nitrogencontaining polybasic polymer source for application to said auxinsusceptible plants.

Other objects and features will be in part apparent and in part pointedout hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph depicting the percent of spray volume for prior artcompositions and compositions of the present invention having dropletparticle sizes of less than 150 microns and less than 100 micronswherein the prior art and inventive composition solutions containedabout 0.56 weight percent acid equivalent dicamba and were sprayed at165 kPa pressure by means of a flatfan 9501E nozzle.

Corresponding reference characters indicate corresponding partsthroughout the drawings.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the present invention, auxin herbicide formulationsexhibiting low volatility, controlled droplet particle size, reducedphysical and reduced vapor drift are provided. As compared to auxinformulations known in the art, it is believed that the formulations ofthe present invention provide enhanced protection from crop injury toauxin tolerant or resistant crops while maintaining comparably effectiveherbicidal efficacy on unwanted plants located in the target area.Throughout the remainder of the description of the invention, wherereference to the auxin herbicide dicamba is made, one skilled in the artwill understand that the principles of the present invention applygenerally to auxin herbicides, including those described above, and theinvention is not limited to dicamba herbicidal formulations.

In some embodiments of the present invention, formulations and methodsare provided that effectively control auxin herbicide release to giveboth commercially acceptable weed control and a commercially acceptablerate of crop injury. In some other embodiments, the formulations provideenhanced crop protection in over the top application to plants.

In accordance with the present invention, a “commercially acceptablerate of weed control” varies with the weed species, degree ofinfestation, environmental conditions, and the associated crop plant.Typically, commercially effective weed control is defined as least about60%, 65%, 70%, 75%, 80%, 85%, 90%, 90%, 95% or even greater than 95%.Although it is generally preferable from a commercial viewpoint that80-85% or more of the weeds be destroyed, commercially significant weedcontrol can occur at much lower levels, particularly with some verynoxious, herbicide-resistant plants. “Weed control,” as used herein,refers to any observable measure of control of plant growth, which caninclude one or more of the actions of (1) killing, (2) inhibitinggrowth, reproduction or proliferation, and (3) removing, destroying, orotherwise diminishing the occurrence and activity of plants. Weedcontrol can be measured by any of the various methods known in the art.For example, weed control can be determined as a percentage as comparedto untreated plants following a standard procedure wherein a visualassessment of plant mortality and growth reduction is made by oneskilled in the art specially trained to make such assessments. Inanother control measurement method, control is defined as an averageplant weight reduction percentage between treated and untreated plants.Preferably, commercial weed control is achieved at no greater than 30days after treatment (DAT), such as from 18 to 30 DAT.

A “commercially acceptable rate of crop injury” for the presentinvention likewise varies with the crop plant species. Typically, acommercially acceptable rate of crop injury is defined less than about20%, 15%, 10% or even less than about 5%. Crop damage can be measured byany means known in the art, such as those describe above for weedcontrol determination. Preferably, crop damage appears no more than from10% to 20% at no greater than 30 DAT, such as from 3 to 21 or from 3 to30 DAT.

The auxin-susceptible plants can be weeds or crop plants. Crop plantsinclude, for example, vegetable crops, grain crops, flowers, root cropsand sod. Crop plants of the present invention include hybrids, inbreds,and transgenic or genetically modified plants.

In some embodiments, the crop plants are auxin tolerant species that arenot susceptible to auxin herbicides or are a transgenic species thatcontain an auxin (e.g., dicamba) resistant trait. Examples includedicamba resistant corn, cotton or soybean. Dicamba resistant crops canfurther comprise one or more additional traits including, withoutlimitation: herbicide resistance (e.g., resistance to other auxinherbicides (e.g., 2,4-D or fluroxypyr), glyphosate, glufosinate,acetolactate synthase inhibitor herbicides (e.g., imazamox, imazethapyr,imazaquin and imazapic), acetyl CoA carboxylase inhibitors (e.g.,sethoxydim and clethodim), etc.); insect resistance such as Bacillusthuringiensis (Bt); high oil; high lysine; high starch; nutritionaldensity; and/or drought resistance. In some other embodiments, the weedsand/or crop plants are glyphosate tolerant or contain a glyphosateresistant trait. Examples include glyphosate resistant corn, cotton orsoybean. In other embodiments, the crop plants comprise stacked traitssuch as dicamba and glyphosate resistance; dicamba and glufosinateresistance; dicamba and acetolactate synthase (ALS) or acetohydroxy acidsynthase (AHAS) resistance; dicamba, glyphosate and glufosinateresistance; dicamba, glyphosate and ALS or AHAS resistance; dicamba,glufosinate and ALS or AHAS resistance; or dicamba, glyphosate,glufosinate and ALS or AHAS resistance. In other embodiments, the plantscan additionally include other herbicide, insect and disease resistancetraits, as well as combinations of those traits. For instance, theplants can have dicamba, 2,4-D or fluroxypyr resistant traits.

In some embodiments, low volatility commercially acceptable formulationsof auxin herbicides are achieved by combining 2,4-D, 2,4-DB,dichloroprop, MCPA, MCPB, aminopyralid, clopyralid, fluroxypyr,triclopyr, diclopyr, mecoprop, mecoprop-P, dicamba, picloram,quinclorac, aminocyclopyrachlor, agriculturally acceptable salts of anyof these herbicides, racemic mixtures or resolved isomers thereof, ormixtures thereof (i) in aqueous solution with one or more solublepolybasic polymers such as, for example, a polymeric polyamine and/or(ii) by raising the pH of aqueous solutions thereof. Cations for theformation of auxin herbicide salts include, without limitation, sodium,potassium, ammonium, lithium, diammonium, monoethanolamine,diethanolamine, triethanolamine, triisopropanolamine, dimethylamine,diethylamine, triethylamine, methylamine, ethylamine, diglycolamine,propylamine, butylamine, pentylamine, hexylamine, heptylamine,octylamine, decylamine and dodecylamine, and mixtures thereof.

In accordance with the present invention, it has yet been furtherdiscovered that the concentration of volatilized auxin herbicide in thevapor phase surrounding a low volatility auxin herbicide formulationcomprising an auxin herbicide salt and one or more polybasic polymers isless than the concentration of volatilized auxin herbicide in the vaporphase surrounding a reference formulation formulated in the absence ofthe polybasic polymer(s), but otherwise having the same formulation asthe low volatility auxin herbicide formulation. Based on experimentalevidence, the concentration of volatilized dicamba herbicide in thevapor phase surrounding the low volatility dicamba herbicideformulations of the present invention comprising a polybasic polymer hasbeen discovered to be less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2or 0.1 that of the concentration of volatilized dicamba herbicide in thevapor phase surrounding a similarly formulated reference formulation butnot containing the polybasic polymer.

Volatilization can be measured by means known to those skilled in theart such as by distilling auxin herbicide compositions and analyzing thedistillation condensate and/or distilled composition for auxin content.In another method, a gas stream can be passed over auxin formulationsinto which the auxin herbicide volatilizes from the formulation. The gasstream can then be quantitatively analyzed for dicamba content bymethods known in the art.

In is believed, without being bound to any particular theory, thatpolybasic polymers reduce auxin salt volatility because dissociatedauxin salt forms ionic bonds with the polybasic polymer and binds theauxin in solution. Any residue from a herbicidal application of theauxin, is therefore inhibited from dissociating to the free acid. In thecase of dicamba, the free acid is about 100 times more volatile thanbound dicamba acid or salt. Furthermore, it is believed that additionallocalization of an auxin in or around the polymer matrix may be achievedthrough cation-pi complexation. It is known that ammonium salts formstable cation-pi complexes with the pi systems of aromatic rings. Inthis case, the ammonium ions of the polymer can form cation-pi orpi-cation-pi complexes with the auxin. This additional complexinteraction may further contribute to reduction in volatilization of theauxin. In some embodiments, reduced dicamba volatility in combinationwith relatively fast dicamba release from the polymer can be achieved byformulating dicamba salts with a polybasic polymer having a relativelyweak ion exchange capability. It is believed that low ion exchangecapacity polymers retard dicamba salt disassociation to the free acidform thereby reducing volatility, but those polymers do not bind thedicamba strongly enough to retard release rate to an extent thatefficacy is reduced. It is further believed that dicamba bound topolymers having relatively strong ion exchange capability would likewisehave a reduced volatilization rate as compared to a similarly formulatedformulation, but not containing the polymer.

Experimental evidence to date indicates that the polymers do not inhibitdicamba herbicidal effectiveness (i.e., do not decrease the availabilityof the herbicide to the plant). Even with the auxin herbicide moleculeheld by either an acid-base and/or cation-pi electron complex, it hasbeen discovered that the biological activity of dicamba is increased ascompared to application of the herbicide with no surfactant and is, infact, generally equivalent to application of the herbicide with asurfactant. This suggests that polymers may increase the availability ofdicamba to the plant.

It has been discovered, in some embodiments of the present invention,that polybasic polymers are effective auxin herbicide drift controlagents because these polymers, when utilized in aqueous auxinformulations, can reduce the number of spray drops having a diameter ofless than about 200 microns, 150 microns, or even 100 microns. It isbelieved, without being bound to any particular theory, that in additionto reducing auxin volatility, polybasic polymers also function asthickeners or rheological property modifying agents that increasesolution viscosity resulting in a greater number of large spray dropletparticles in the size distribution and restricting the generation ofsmall droplet particles. For a given velocity, wind will move largedroplet particles a shorter distance as compared to smaller dropletparticles. Notably, an increase in average spray drop size from about 10microns to about 150 microns can decrease the lateral distance a dropletparticle travels in a light wind after normal spraying by about 300 to500 meters. Spray droplet particle size can be measured by methods knownto those skilled in the art such as phase doppler droplet particleanalysis (PDPA).

In order to achieve the benefits of reduced auxin volatility and/orenhanced auxin drift control, polybasic polymers, having from 4 to about100,000 nitrogen atoms per molecule, from about 15 to about 100,000nitrogen atoms per molecule, from about 25 to about 100,000 nitrogenatoms per molecule, from about 50 to about 100,000 nitrogen atoms permolecule, or even from about 100 to about 100,000 nitrogen atoms permolecule, or mixtures of polybasic polymers having an average number ofnitrogen atoms within the above ranges, are preferred. For polybasicpolymers or a combination of polymers, an average nitrogen content offrom 10% to about 50% by weight, from 13% to about 50%, from 15% toabout 50%, from about 20% to about 50%, from about 30% to about 45% byweight, or even about 30% to about 40% by weight is preferred. Examplesof typical polymer molecular weights, or average molecular weight forpolymer mixtures, (in Daltons) for the practice of the present inventioninclude 600, 800, 1,300, 1,500, 2,000, 2,500, 5,000, 10,000, 20,000,50,000, 75,000, 100,000, 250,000, 500,000, 750,000, 1,000,000,1,250,000, 1,500,000, 1,750,000, 2,000,000, 2,250,000, 1,500,000,1,750,000, 2,000,000, 2,250,000, 2,500,000, 2,750,000 or even 3,000,000,and ranges thereof. Polybasic polymers suitable for the practice of thepresent invention are preferably hydrophilic and have an aqueoussolubility of at least 5% v/v, more preferably at least 10% v/v.

Formulations comprising an auxin herbicide salt are generally compatiblewith polybasic polymers in tank mixes as well as in concentrateformulations. Advantageously therefore, the polybasic polymers of thepresent invention do not require separate addition into a spray tank.Alternatively however, the polybasic polymers of the present inventioncan be combined with auxin herbicide formulations before use on plantssuch as by addition to auxin herbicide concentrate compositions or auxinherbicide tank mixes, or by introducing an auxin herbicide compositionand a polybasic polymer or polymer combination as separate feed streamsto a spraying or application system so that the feed streams areco-mixed immediately prior to use. A weight ratio of dicamba acidequivalent (a.e.) to polybasic polymer or combination of polymers offrom 1:100 to about 100:1, from about 1:50 to about 50:1, from about 1:1to about 100:1, from about 1:1 to about 50:1, from about 1:1 to about25:1, from about 1:1 to about 10:1, from about 3:1 to about 10:1 or fromabout 5:1 to about 10:1 is preferred. In some embodiments of the presentinvention, formulations contain from about 1% to about 10% v/v totalpolybasic polyamine and from about 360 to about 750, from about 400 toabout 750, from about 450 to about 750, from about 460 to about 750,from about 470 to about 750, from about 480 to about 750, from about 490to about 750, or from about 500 to about 750 grams a.e. per liter (ga.e./L) dicamba.

Combinations of the above-described polymer nitrogen content, molecularweights, solubilities, concentrations and ratios are within the scope ofthe present invention.

Auxin herbicide salts are generally preferred as compared to the acidform for combination with polybasic polymers. Suitable cations for auxinherbicide salts include, for example and without restriction, DMA, MEA,DEA, triethanolamine (TEA), potassium, sodium, IPA and DGA. In someembodiments of the present invention, the auxin herbicide component ofthe formulation consists essentially of auxin herbicide salts. Indicamba embodiments, MEA, DEA and potassium dicamba are preferredbecause they are believed to be compatible with polybasic polymers suchas polymeric polyamines, such that high concentrations in aqueoussolution can be achieved while volatility is low as compared to otherdicamba salt formulations that do not contain the polymer and withoutrequiring the pH of the formulation to be 9 or greater.

In other embodiments, in the case of dicamba, low volatility can beachieved by formulating dicamba as the monoethanolamine ordiethanolamine salt. It has been discovered that the MEA anddiethanolamine (DEA) salts of dicamba are less volatile than otherdicamba salts, such as the DMA and IPA salts, known in the art. Inparticular, the concentration of volatilized dicamba in the vapor phasesurrounding the aqueous dicamba MEA or DEA concentrate formulation isless than the concentration of volatilized dicamba in the vapor phasesurrounding a reference formulation formulated from dicamba salts knownin the art such as dimethylamine dicamba, isopropylamine dicamba, ormixtures thereof, but otherwise having the same composition as thedicamba MEA concentrate formulation. Distillation studies of solutionsof the MEA, sodium, potassium, DGA and IPA dicamba salts show thatdicamba salts having relatively volatile cations, such as or IPA, havecomparably greater dicamba volatilization than do dicamba salts havingless volatile cations, such as sodium, potassium, MEA or DEA. Theconcentration of volatilized dicamba herbicide in the vapor phasesurrounding an MEA dicamba formulation has been discovered to be from0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or ranges thereof,that of the concentration of volatilized dicamba herbicide in the vaporphase surrounding similarly formulated IPA dicamba. Experimentalmeasurements of dicamba concentration in the gas phase above dicambasalt aqueous solutions show that the gas phase dicamba concentrationassociated with an MEA dicamba aqueous solution is typically less thanthe gas phase concentration associated with a comparative solution ofdicamba acid or the IPA or DMA dicamba salts, wherein the comparativesolution otherwise has the same formulation as the MEA dicamba saltsolution. In particular, it has been discovered that the gas phasedicamba concentration associated with MEA dicamba is about 2, 5, 10, 15or 20 times less than the gas phase dicamba concentration associatedwith DMA dicamba and about 7 to 8 times less than the gas phase dicambaconcentration associated with IPA dicamba in otherwise similarlyformulated formulations.

It is further believed that the amount of dicamba volatilizing from anaqueous solution of the sodium, potassium, MEA or DEA salt can also be afunction of pH, with volatilization varying inversely with pH. Ingeneral, dicamba volatility decreases with increasing pH. Without beingbound to any particular theory and based on experimental evidence todate, the pH dependent trend may be explained by theHenderson-Hasselbalch equation, (pH=pKa+log [HA/A−]) where HA representsthe concentration of acidic species with an associated hydrogen and A⁻represents the concentration of the deprotonated basic species. As thepH is increased, there is more ionization of dicamba acid (moredissociation) resulting in a lower vapor pressure. This helps to explainthe disparity observed in the volatility between dicamba acid and thedicamba salts, and also the difference in volatility between salts atlow pH versus salts at high pH. The increased ionization with the saltsand the increased dissociation at the higher pHs may lead to a lowervapor pressure and therefore lower volatility. A pH of from about 4 toabout 11, from about 5 to about 10, or from about 7 to about 9 ispreferred for any of the various dicamba salts. It is believed that thepolybasic polymers of the present invention function as pH buffersthereby maintaining a nearly constant pH value in the dicambacompositions of the present invention, even upon the addition of a smallamount of acid. The buffering effect therefore assists in maintaininglow vapor pressure and low volatility by resisting pH changes into theacidic range.

In accordance with the present invention, and based on experimentalevidence, it has been further discovered that the monoethanolamine (MEA)salt of dicamba provides higher aqueous solubility and lower viscosityas compared to dicamba acid and other dicamba salts known in the art,such as the dimethylamine (DMA) and isopropylamine (IPA) salts. Asindicated in Table A below, MEA salt aqueous solubility at 20° C. isabout 66.1 weight percent a.e. (wt % a.e.), or about 885 grams acidequivalent per liter (g a.e./L) as compared to 54.6 wt % a.e. (720 ga.e./L) and 56.5 wt % a.e. (700 g a.e./L) for potassium dicamba anddiglycolamine (DGA) dicamba, respectively. The DMA salt of dicamba isbelieved to have a solubility at 20° C. of about 45 wt % a.e. (600 ga.e./L).

TABLE A wt % a.e. Approximate g a.e./L Dicamba @20° C. @20° C. acid 0.44.5 sodium salt 36.3 364 potassium salt 54.6 720 DGA salt 56.5 700 MEAsalt 66.1 885

In some embodiments of the present invention, MEA, potassium and DEAdicamba tank mix formulations are provided. The tank mix formulationspreferably comprise from about 0.1 to about 50 g a.e./L, such as 0.1,0.5, 1, 5, 10, 25 or 50 g a.e./L, and ranges thereof.

In some other embodiments, of the present invention, MEA dicambaconcentrate formulations are provided. The concentrate formulationspreferably comprise at least 50 g a.e./L, such as from about 50 to about885, from about 100 to about 885, from about 200 to about 885, fromabout 300 to about 885, from about 400 to about 885, from about 500 toabout 885, from about 550 to about 885, or from about 600 to about 885 ga.e./L MEA dicamba. For example, 50, 100, 150, 200, 250, 300, 350, 400,450, 500, 550, 600, 650, 700, 750, 800, 850 or 885 g a.e./L, and rangesthereof.

In some other embodiments, of the present invention, potassium dicambaconcentrate formulations are provided. The concentrate formulationspreferably comprise at least 550 g a.e./L, such as from about 550 toabout 720, or from about 600 to about 720 g a.e./L potassium dicamba.For example, 550, 600, 650, 700 or 720 g a.e./L, and ranges thereof.

In some other embodiments, of the present invention, DEA dicambaconcentrate formulations are provided. The concentrate formulationspreferably comprise at least 50 g a.e./L, from about 50 to about 720,from about 100 to about 720, from about 200 to about 720, from about 300to about 720, from about 400 to about 720, from about 500 to about 720,from about 550 to about 720, or from about 600 to about 720 g a.e./L DEAdicamba. For example, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500,550, 600, 650, 700, or 720 g a.e./L, and ranges thereof.

In still other embodiments of the present invention, mixed dicamba saltcompositions comprising at least one of the MEA, DEA or potassium saltare provided. In addition to the MEA, DEA and potassium dicamba salts,suitable salts include the sodium, ammonium, lithium, diammonium,triethanolamine, triisopropanolamine, DMA, diethylamine, triethylamine,methylamine, ethylamine, DGA, propylamine (such as IPA or n-propyl),butylamine, pentylamine, hexylamine, heptylamine, octylamine,dodecylamine and decylamine dicamba salts. More preferably, the mixedsalts include two or more dicamba salts selected from the MEA, DEA,sodium, potassium, IPA, DGA and DMA salts, wherein at least one salt isthe MEA, DEA or potassium salt of dicamba. A weight ratio of the MEA,DEA and/or potassium dicamba salt to the sum of the other salts of nogreater than about 20:1, such as 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5,1:10 and ranges thereof, is preferred, more preferably from 20:1 toabout 1:10, from about 20:1 to about 1:5, from about 20:1 to 1:1, orfrom about 20:1 to about 5:1. The total dicamba concentration for themixed salt compositions on an acid equivalent basis is at least about52.5, 100, 150, 200, 250, 300, 350, 400, 450, 480, 500, 520, 540, 560,575, 580, 600, 620, 640, 660, 680 or 700 grams per liter, and rangesthereof. For any given dicamba salt and concentration thereof, oneskilled in the art can readily determine using routine experimentation aminimum ratio of the dicamba salts (i.e. a lower limit from the upperlimit of 20:1) that is necessary to achieve the objects of the inventionin view of the other components of the formulation, such as aco-herbicide component, polybasic polymer component and/or surfactantcomponent and their respective concentrations.

It has yet been further discovered that MEA dicamba concentrateformulations are only moderately irritating to eyes at a pH of about 8.Eye irritation measurement can be done according to the methods providedin U.S. Environmental Protection Agency Office of Prevention, Pesticidesand Toxic Substances, Health Effects Test Guidelines (for example, OPPTS870.2400 Acute Eye Irritation, August 1998). MEA dicamba formulationsare generally classified in the eye irritation (rabbit) FIFRA (FederalInsecticide, Fungicide and Rodenticide Act) category III (moderateirritation).

In some embodiments of the present invention, the polybasic polymer is apolymeric polyamine, polymeric polyimine, nitrogen-substituted vinylpolymer, polyoxazoline, polymeric polypeptide, polymeric polyimide,polypropyleneimine dendrimer, polyethyleneimine dendrimer or apolyamidoamine dendrimer. Combinations thereof are also within the scopeof the present invention.

In some embodiments of the present invention, the polybasic polymer is apolymeric polyamine. Polymeric polyamines include, for instance,polyethyleneimines, polyalkoxylated polyamines, and combinationsthereof. Particular polymeric polyamines include benzylated polyamines,ethoxylated polyamines, propoxylated polyamines, alkylated polyamines,esterified polyamines and combinations thereof.

In some embodiments of the present invention, the polymeric polyamineshave structure (1):

wherein each R₁ is independently hydrogen, a hydrocarbyl or substitutedhydrocarbyl group having from 1 to 20 carbon atoms, an aryl group, or acyclic group; each R₂ is independently an alkylene having from 1 to 4carbon atoms or an aryl, each R₃ is independently hydrogen or ahydrocarbyl having from 1 to 4 carbon atoms and x is a degree ofpolymerization of from about 1 to about 70,000. R₁ is preferablyindependently hydrogen or an alkyl having from 1 to 12 carbon atoms, R₂is preferably independently ethylene or C₆ arylene, R₃ is preferablyindependently hydrogen or an alkyl having from 1 to 4 carbon atoms and xis preferably selected to give a linear polyimine having a molecularweight of from 600 to 3,000,000 Daltons. Examples of polymericpolyamines include polyaniline wherein R₂ is C₆ arylene and R₃ ishydrogen and poly(ethylene imine) wherein R₂ is ethylene and R₃ ishydrogen

In some embodiments of the present invention, the polymeric polyamine isa polymeric polyimine compound (hereafter referred to as “polyimines”)selected from linear polyimines and branched polyimines having amolecular weight of from about 800 to about 3,000,000 Daltons.

Linear polyimines typically have structure (2):

wherein each R₁₀ is independently hydrogen, a hydrocarbyl or substitutedhydrocarbyl group having from 1 to 20 carbon atoms or an aryl group;each R₂₀ is independently an alkylene having from 1 to 4 carbon atoms;each R₃₀ is independently hydrogen or a hydrocarbyl having from 1 to 4carbon atoms wherein R₃₀ substitution occurs at any of the R₂₀ carbonatoms; and x is a degree of polymerization of from about 1 to about70,000. R₁₀ is preferably independently hydrogen or an alkyl having from1 to 12 carbon atoms, R₂₀ is preferably ethylene, R₃₀ is preferablyindependently hydrogen or an alkyl having from 1 to 4 carbon atoms and xis preferably selected to give a linear polyimine having a molecularweight of from 800 to 3,000,000 Daltons.

Branched polyimines typically have structure (3):

wherein each R₁₀ is independently hydrogen, a hydrocarbyl or substitutedhydrocarbyl group having from 1 to 20 carbon atoms or an aryl group;each R₂₀ is independently an alkylene having from 1 to 4 carbon atoms;and y is a degree of polymerization of from about 1 to about 70,000.Each R₃₀ is independently hydrogen or an amine of formula (4):

—R₄₀—NR₄R₄₂  (4)

wherein at least one R₃₀ is of formula (4) and wherein R₄₀ is analkylene having from 1 to 4 carbon atoms, and R₄₁ and R₄₂ areindependently selected from hydrogen, a hydrocarbyl or substitutedhydrocarbyl having from 1 to 20 carbon atoms, and an amine of formula(5):

wherein R₅₀ is an alkylene having from 1 to 4 carbon atoms, R₅₁ and R₅₂are independently selected from hydrogen and a hydrocarbyl orsubstituted hydrocarbyl having from 1 to 20 carbon atoms, and each z isindependently from 0 to 5. R₅₀ is preferably ethylene, R₅₁ and R₅₂ arepreferably independently hydrogen or a hydrocarbyl having from 1 to 12carbon atoms. The sum of y and z are preferably selected to give abranched polyimine having a molecular weight of from 800 to 3,000,000Daltons.

Also included within the scope of polymeric polyimines are polynitrilesof structure (6):

wherein each R₆₀ is independently hydrogen, a hydrocarbyl or substitutedhydrocarbyl group having from 1 to 20 carbon atoms or an aryl group;each R₆₁ is independently hydrogen or a hydrocarbyl having from 1 to 6carbon atoms; and x is a degree of polymerization of from about 1 toabout 70,000 selected to yield a molecular weight of from 600 to3,000,000 Daltons.

Representative polyimines and polymeric polyimines include, but are notlimited to, compounds of structures (7) and (8):

wherein x is the degree of polymerization. Formula (8) is generallyrepresentative of Lupasol® polyimine polymers available from BASF.

Representative commercially available polyimines are shown in Table Bbelow where Epomin® is commercially available from Aceto Corp.; “MW”refers to the average molecular weight in Daltons; “Visc.” refers toviscosity in mPa at 20° C.; “Pour Pt.” refers to the pour point in ° C.;“Density” refers to the density in grams per mL measured at 20° C.; and“Ratio” refers to the ratio of primary:secondary:tertiary aminenitrogens:

TABLE B Polyimine MW Visc. Pour Pt. Density Ratio LUPASOL FG 800 800 −31.09 1:0.82:0.53 LUPASOL 20 wfr 1,300 5,000 −16 1.03 1:0.91:0.64 LUPASOLPR 8515 2,000 75,000 −9 1.05 1:0.92:0.70 LUPASOL WF 25,000 200,000 −31.1  1:1.2:0.76 LUPASOL FC 800 250 −24 1.08 1:0.86:0.42 LUPASOL G201,300 350 −24 1.08 1:0.9:0.64 LUPASOL G35 2,000 450 −18 1.08 1:0.94:0.67LUPASOL G100 5,000 1,200 −18 1.08 1:1.05:0.76 LUPASOL G500 25,000 1,000No Data No Data No Data LUPASOL HF 25,000 14,000 −20 1.08 1:1.2:0.76LUPASOL P 750,000 500,000 −3 1.09 1:1.07:0.77 LUPASOL PS 750,000 1,400−5 No Data 1:1.07:0.77 LUPASOL SK 2,000,000 750 0 1.06 No Data LUPASOLSNA 1,000,000 500 0 1.06 No Data LUPASOL HEO1 13,000 200 No Data No DataNo Data LUPASOL PN50 1,000,000 6,000 No Data NoData No Data LUPASOLPO100 5,000 300 No Data NoData No Data EPOMIN 006 600 No Data No DataNoData No Data EPOMIN 012 1,200 No Data No Data NoData No Data EPOMIN018 1,800 No Data No Data NoData No Data EPOMIN 1000 100,000 No Data NoData NoData No Data Aldrich 408727 25,000 No Data No Data 1.03 No Data

In some embodiments, polyalkylenimines can be functionalized by reactionwith one or more alkylene oxides to form the hydroxyalkylatedderivative. As described in U.S. Pat. No. 7,431,845 (to Manek et al.), ahydroxyalkylated derivative may be prepared by heating an aqueoussolution of polyalkylenimine with the desired amount of alkylene oxideat a temperature of about 80° C. to about 135° C., optionally in thepresence of an alkali metal catalyst such as sodium methoxide, potassiumtert-butoxide, potassium or sodium hydroxide. In some embodiments, thepolyalkylenimine is functionalized by reaction with ethylene oxideand/or optionally propylene oxide. In other embodiments, thepolyalkylenimine is functionalized by reaction with about 1 to about 100molar equivalents of ethylene oxide per ethylene unit in thepolyalkylenimine. In still other embodiments, the polyalkylenimine isfunctionalized by reaction with about 1 to about 100 molar equivalentsof ethylene oxide and about 1 to about 100 molar equivalents ofpropylene oxide per ethylene unit in the polyalkylenimine. In yet otherembodiments, the polyalkylenimine is reacted first with the propyleneoxide and subsequently with the ethylene oxide. For example, in someembodiments, the polyalkylenimine is functionalized by reaction withabout 5 to about 25 molar equivalents of ethylene oxide and about 85 toabout 98 molar equivalents of propylene oxide per ethylene unit in thepolyalkylenimine.

Examples of commercial oxyalkylated polyalkylenimines include LupasolSC-61B and Lupasol SK (available from BASF), and Kemelex 3550X, 3423X,3546X, D600 and 3582X (available from Uniquema, New Castle, Del., USA).

Lupasol SC-61B is believed to be a hydroxylated (ethoxylated)polyethylenimine of formula (9):

wherein R₉₀ is hydrogen or a continuation of the polymer chain and x isa value required to yield a molecular weight of about 110,000 Daltons.

In some embodiments of the present invention the polybasic polymers aredendritic polymers (for example, starburst polymers), characterized asrepeatedly branched molecules having attached functional groupsdistributed on the periphery of the branches thereby providing a highlyfunctionalized surface. Preferred dendritic polymers arepolypropyleneimine dendrimers, polyethyleneimine dendrimers, andpolyamidoamine dendrimers. A molecular weight of from about 1000 toabout 1,000,000 is preferred, representing from 1 to about 10 generationgrowth steps.

In some embodiments of the present invention, the polybasic polymer is anitrogen-substituted vinyl polymer.

Vinyl polymers include polyvinyl acrylamides of formula (10):

wherein each R₁₀₀ is independently hydrogen, a hydrocarbyl orsubstituted hydrocarbyl group having from 1 to 20 carbon atoms or anaryl group; R₁₀₁ is a nitrogen-containing moiety; and x is a degree ofpolymerization of from about 1 to about 70,000. In some embodiments,R₁₀₁ is acrylamide (—C(O)NH₂), allylamine (—CH₂NH₂), pyridine, pyrazine,pyrazole or pyrazoline. The polyacrylamides can comprise cationicmonomers such as, for example, dimethyl aminoethyl acrylate methylchloride, dimethyl aminoethyl methacrylate methyl chloride,acrylamidopropyl trimethyl ammonium chloride, methacryl amodopropyltrimethyl ammonium chloride, and diallyl dimethyl ammonium chloride.Examples of vinyl polymers include poly(vinyl pyridine), depicted informula (12) comprising the monomer poly(2-vinyl pyridine):

and polyvinyl acrylamide comprising the monomer depicted in formula(13):

In some other embodiments of the present invention, the polybasicpolymer is a polyamide.

Polyamide polymers include polymeric acrylamides comprising therepeating unit of general formula (14):

wherein each R₁₄₀ is independently hydrogen or a hydrocarbyl having from1 to 6 carbon atoms, each R₁₄₁ is independently alkylene having from 1to 8 carbon atoms or arylene, each r is independently 0 or 1, and x is adegree of polymerization of from about 1 to about 70,000.

Examples of polyamide polymers include polyisocyanates comprising therepeating unit of formula (15):

and polylactams comprising the repeating unit of formula (16):

wherein m is from 1 to 6.

In some other embodiments of the present invention, the polybasicpolymer material is a polyoxazoline comprising the repeating unit offormula (17):

wherein R₁₇₀ is a substituted or unsubstituted alkylene group containing1 to about 4 carbon atoms; R₁₇₁ is a hydrocarbyl or substitutedhydrocarbyl that does not significantly decrease the water-solubility ofthe polymer; and n is an integer which provides the polymer with amolecular weight of from 600 to 3,000,000 Daltons. R₁₇₀ may besubstituted with hydroxy, amide or polyether. R₁₇₀ is preferablymethylene, ethylene, propylene, isopropylene or butylene. R₁₇₀ is mostpreferably ethylene. R₁₇₁ is preferably alkyl or aryl; R₁₇₁ may besubstituted with hydroxy, amide or polyether. Preferably R₁₇₁ is methyl,ethyl, propyl, isopropyl, butyl, or isobutyl. Most preferably R₁₇₀ isethylene and R₁₇₁ is ethyl.

In some other embodiments of the present invention, the polybasicpolymer is a polymeric polypeptide (poly α-amino acid) comprising therepeating unit of formula (18):

wherein each R₁₈₀ is independently selected from a side chain specificto amino acids, indicated in parentheses below. For instance, R₁₈₀ maybe hydrogen (glycine), —CH₃ (alanine), —CH(CH₃)₂ (valine), —CH₂CH(CH₃)₂(leucine), —CH(CH₃)(CH₂CH₃) (isoleucine), —(CH₂)₄NH₂ (lysine), —CH₂OH(serine), —CH(OH)(CH₃) (threonine), etc., and x is selected to provide amolecular weight between 600 and 3,000,000 Daltons. In some embodiments,polar R₁₈₀ groups are preferred to provide greater water solubility.Polar amino acids include arginine, aspargine, aspartic acid, cysteine(slightly polar), glutamic acid, glutamine, histidine, lysine, serine,threonine, tryptophan (slightly polar) and tyrosine.

Any of the polymers described above for formulae (7) through (18) can beterminated with a head group independently selected from hydrogen, ahydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbonatoms or an aryl group.

In some embodiments of the present invention, surfactants can optionallybe used in auxin herbicide formulations to effectively enhanceherbicidal effectiveness. In some other embodiments, solubilizers can beoptionally be used to enhance polybasic polymer aqueous solubility. Insome embodiments, a compound can function as both an efficacy enhancerand a solubilizer. Typically, at low concentrations relative to theauxin herbicide component (i.e., a high weight ratio of auxin a.e. tosurfactant, for example in excess of about 20:1), such compounds mayenhance polybasic polymer solubility but not effectively provideherbicidal efficacy enhancement. Conversely, at higher concentrationsrelative to the auxin herbicide component, such compound may bothenhance herbicidal efficacy and polyamine polymer solubility.

Surfactants are optionally included in auxin (dicamba) formulations tofacilitate dicamba retention, uptake and translocation into the plantfoliage and thereby enhance herbicidal effectiveness. It has beendiscovered that the polymeric polyamines of the present invention are atleast as effective as surfactants for foliar retention, uptake andtranslocation of dicamba. Efficacious dicamba formulations containingpolymeric polyamines or other polybasic polymers, with or without asurfactant, are therefore within the scope of the present invention.

In some embodiments of the present invention, one or more herbicidalefficacy enhancing surfactants known in the art can optionally beformulated with dicamba. It has been discovered that MEA dicambaformulations are compatible with most water soluble surfactants. Aweight ratio of dicamba a.e. to surfactant of from 1:1 to 20:1. from 2:1to 10:1 or from 3:1 to 8:1 is preferred.

Alkoxylated tertiary etheramine surfactants for use in the herbicidalformulations of the present invention have the general structure (19):

wherein R₁₉₁ is a hydrocarbyl or substituted hydrocarbyl having fromabout 4 to about 22 carbon atoms; each R₁₉₂ is a hydrocarbyleneindependently having 2, 3, or 4 carbon atoms; m is an average numberfrom about 1 to about 10; R₁₉₃ and R₁₉₄ are each independentlyhydrocarbylene having 2, 3, or 4 carbon atoms; and the sum of x and y isan average value ranging from about 2 to about 60.

R₁₉₁ is preferably an alkyl having from about 4 to about 22 carbonatoms, more preferably from about 8 to about 18 carbon atoms, from about10 to about 16 carbon atoms, or from about 12 to about 18 carbons atoms,or from about 10 to about 14 carbon atoms. Sources of the R₁₉₁ groupinclude, for example, coco or tallow, or R₁₉₁ may be derived fromsynthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl,hexadecyl, or octadecyl groups. Each R₁₉₂ may independently bepropylene, isopropylene, or ethylene, and m is preferably from about 1to 5, such as 2 to 3. R₁₉₃ and R₁₉₄ may be ethylene, propylene,isopropylene, and are preferably ethylene. The sum of x and y ispreferably an average value ranging from about 2 to about 22, such asfrom about 2 to 10, or about 2 to 5. In some embodiments, the sum of xand y is preferably between about 10 and about 20, for example, about15.

Specific alkoxylated tertiary etheramine surfactants for use in theherbicidal formulation of the present invention include, for example,any of the TOMAH E-Series surfactants, such as TOMAH E-14-2(bis-(2-hydroxyethyl) isodecyloxypropylamine), TOMAH E-14-5 (poly (5)oxyethylene isodecyloxypropylamine), TOMAH E-17-2, TOMAH E-17-5 (poly(5) oxyethylene isotridecyloxypropylamine), TOMAH E-19-2, TOMAH E-18-2,TOMAH E-18-5 (poly (5) oxyethylene octadecylamine), TOMAH E-18-15, TOMAHE-19-2 (bis-(2-hydroxyethyl) linear alkyloxypropylamine), TOMAH E-S-2,TOMAH E-S-15, TOMAH E-T-2 (bis-(2-hydroxyethyl) tallow amine), TOMAHE-T-5 (poly (5) oxyethylene tallow amine), and TOMAH E-T-15 (poly (15)oxyethylene tallow amine). Another example is Surfonic AGM 550 availablefrom Huntsman Petrochemical Corporation wherein, for formula (9), R₁₉₁is C₁₂₋₁₄, R₁₉₂ is isopropyl, m is 2, R₁₉₃ and R₁₉₄ are each ethylene,and x+y is 5.

Alkoxylated quaternary etheramine surfactants for use in the herbicidalformulations of the present invention have the general structure (20):

wherein R₂₀₁ is a hydrocarbyl or substituted hydrocarbyl having fromabout 4 to about 22 carbon atoms; Each R₂₀₂ is independently ahydrocarbylene having 2, 3, or 4 carbon atoms; m is an average numberfrom about 1 to about 10; R₂₀₃ and R₂₀₄ are each independentlyhydrocarbylene having 2, 3, or 4 carbon atoms; and the sum of x and y isan average value ranging from about 2 to about 60. R₂₀₅ is preferably ahydrocarbyl or substituted hydrocarbyl having from 1 to about 4 carbonatoms, more preferably methyl. A is a charge balancing counter-anion,such as sulfate, chloride, bromide, nitrate, among others.

R₂₀₁ is preferably an alkyl having from about 4 to about 22 carbonatoms, more preferably from about 8 to about 18 carbon atoms, from about10 to about 16 carbon atoms, or from about 12 to about 18 carbons atoms,or from about 12 to about 14 carbon atoms. Sources of the R₂₀₁ groupinclude, for example, coco or tallow, or R₂₀₁ may be derived fromsynthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl,hexadecyl, or octadecyl groups. Each R₂₀₂ may independently bepropylene, isopropylene, or ethylene, and m is preferably from about 1to 5, such as 2 to 3. R₂₀₃ and R₂₀₄ may be ethylene, propylene,isopropylene, and are preferably ethylene. The sum of x and y ispreferably an average value ranging from about 2 to about 22, such asfrom about 2 to 10, or about 2 to 5. In some embodiments, the sum of xand y is preferably between about 10 and about 20, for example, about15.

Specific alkoxylated quaternary etheramine surfactants for use in theherbicidal formulation of the present invention include, for example,TOMAH Q-14-2, TOMAH Q-17-2, TOMAH Q-17-5, TOMAH Q-18-2, TOMAH Q-S, TOMAHQ-S-80, TOMAH Q-D-T, TOMAH Q-DT-HG, TOMAH Q-C-15, and TOMAH Q-ST-50.

Alkoxylated etheramine oxide surfactants for use in the herbicidalformulations of the present invention have the general structure (21):

wherein R₂₁₁ is a hydrocarbyl or substituted hydrocarbyl having fromabout 4 to about 22 carbon atoms; Each R₂₁₂ is independently ahydrocarbylene having 2, 3, or 4 carbon atoms; m is an average numberfrom about 1 to about 10; R₂₁₃ and R₂₁₄ are each independentlyhydrocarbylene having 2, 3, or 4 carbon atoms; and the sum of x and y isan average value ranging from about 2 to about 60.

R₂₁₁ is preferably an alkyl having from about 4 to about 22 carbonatoms, more preferably from about 8 to about 18 carbon atoms, from about10 to about 16 carbon atoms, or from about 12 to about 18 carbons atoms,or from about 12 to about 14 carbon atoms. Sources of the R₂₁₁ groupinclude, for example, coco or tallow, or R₂₁₁ may be derived fromsynthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl,hexadecyl, or octadecyl groups. R₂₁₂ may be propylene, isopropylene, orethylene, and m is preferably from about 1 to 5, such as 2 to 3. EachR₂₁₃ and R₂₁₄ is independently ethylene, propylene, isopropylene, andare preferably ethylene. The sum of x and y is preferably an averagevalue ranging from about 2 to about 22, such as from about 2 to 10, orabout 2 to 5. In some embodiments, the sum of x and y is preferablybetween about 10 and about 20, for example, about 15.

Specific alkoxylated etheramine oxide surfactants for use in theherbicidal formulation of the present invention include, for example,any of the TOMAH AO-series of surfactants, such as TOMAH AO-14-2, TOMAHAO-728, TOMAH AO-17-7, TOMAH AO-405, and TOMAH AO-455.

Alkoxylated tertiary amine oxide surfactants for use in the herbicidalformulations of the present invention have the general structure (22):

wherein R₂₂₁ is a hydrocarbyl or substituted hydrocarbyl having fromabout 4 to about 22 carbon atoms, R₂₂₂ and R₂₂₃ are each independentlyhydrocarbylene having 2, 3, or 4 carbon atoms, and the sum of x and y isan average value ranging from about 2 to about 50.

R₂₂₁ is preferably an alkyl having from about 4 to about 22 carbonatoms, more preferably from about 8 to about 18 carbon atoms, and stillmore preferably from about 12 to about 18 carbons atoms, for examplecoco or tallow. R₂₂₁ is most preferably tallow. R₂₂₂ and R₂₂₃ arepreferably ethylene. The sum of x and y is preferably an average valueranging from about 2 to about 22, more preferably between about 10 andabout 20, for example, about 15.

Specific alkoxylated tertiary amine oxide surfactants for use in theherbicidal formulations of the present invention include, for example,any of the AROMOX series of surfactants, including AROMOX C/12, AROMOXC/12W, AROMOX DMC, AROMOX DM16, AROMOX DMHT, and AROMOX T/12 DEG.

Alkoxylated tertiary amine surfactants for use in the herbicidalformulations of the present invention have the general structure (23):

wherein R₂₃₁ is a hydrocarbyl or substituted hydrocarbyl having fromabout 4 to about 22 carbon atoms, R₂₃₂ and R₂₃₃ are each independentlyhydrocarbylene having 2, 3, or 4 carbon atoms, and the sum of x and y isan average value ranging from about 2 to about 50.

R₂₃₁ is preferably an alkyl having from about 4 to about 22 carbonatoms, more preferably from about 8 to about 18 carbon atoms, and stillmore preferably from about 12 to about 18 carbons atoms, for examplecoco or tallow. R₁ is most preferably tallow. R₂₃₂ and R₂₃₃ arepreferably ethylene. The sum of x and y is preferably an average valueranging from about 2 to about 22, more preferably between about 10 andabout 20, for example, about 15.

Specific alkoxylated tertiary amine surfactants for use in theherbicidal formulations of the present invention include, for example,Ethomeen T/12, Ethomeen T/20, Ethomeen T/25, Ethomeen T/30, EthomeenT/60, Ethomeen C/12, Ethomeen C/15, and Ethomeen C/25, each of which areavailable from Akzo Nobel.

Alkoxylated quaternary amine surfactants for use in the herbicidalformulations of the present invention have the general structure (24):

wherein R₂₄₁, R₂₄₂, R₂₄₃, x and y are as described above for thealkoxylated tertiary amine surfactants of structure (II), i.e., R₂₄₁ isa hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22carbon atoms, R₂₄₂ and R₂₄₃ are each independently hydrocarbylene having2, 3, or 4 carbon atoms, and the sum of x and y is an average valueranging from about 2 to about 50. R₂₄₄ is preferably a hydrocarbyl orsubstituted hydrocarbyl having from 1 to about 4 carbon atoms, morepreferably methyl. X is a charge balancing counter-anion, such assulfate, chloride, bromide, nitrate, among others.

R₂₄₁ is preferably an alkyl having from about 4 to about 22 carbonatoms, more preferably from about 8 to about 18 carbon atoms, and stillmore preferably from about 12 to about 18 carbons atoms, for examplecoco or tallow. R₂₄₁ is most preferably tallow. R₂₄₂ and R₂₄₃ arepreferably ethylene. The sum of x and y is preferably an average valueranging from about 2 to about 22, more preferably between about 10 andabout 20, for example, about 15. Specific alkoxylated quaternary aminesurfactants for use in the herbicidal formulation of the presentinvention include, for example, Ethoquad T/12, Ethoquad T/20, EthoquadT/25, Ethoquad C/12, Ethoquad C/15, and Ethoquad C/25, each of which areavailable from Akzo Nobel.

An example of an alkoxylated polyamine surfactant for use in theherbicidal formulations of the present invention is a surfactant havingthe general structure (25):

wherein R₂₅₁ is an alkyl or alkenyl radical containing 6 to 25 carbonatoms and from 0 to 3 carbon-carbon double bonds; R₂₅₂ is —OCH₂CH₂CH₂—,—C(═O)OCH₂CH₂—, —C(═O)NHCH₂CH₂CH₂—, or —CH₂—; each occurrence of R₂₅₄ isindependently —H, —OC(═O)R₁, —SO₃ ⁻A⁺ or —CH₂C(═O)O⁻A⁺ wherein A⁺is analkali metal cation, ammonium or H⁺; each occurrence of a is from 3 to8; each R₂₅₃ is independently ethyl, isopropyl or n-propyl; d, e, f andg are each independently from 1 to 20, b is from 0 to 10, c is 0 or 1,the sum of (c+d+e+f) is from (3+b) to 20, and the molecular weight is nomore than about 800. The surfactants of formula (25) can optionally bein the form of a cation where one or more nitrogen atoms is additionallysubstituted with hydrogen, methyl, ethyl, hydroxyethyl or benzyl and oneor more anions, equal in number to the number of said additionallysubstituted nitrogen atoms and being selected from chloride,methylsulfate and ethylsulfate. The surfactants of formula (25) canfurther optionally be in the form of amine oxides.

Examples of specific alkoxylated polyamine surfactants for use in theherbicidal formulation of the present invention are described indescribed in U.S. Pat. No. 6,028,046 (to Arif). Alkoxylated polyaminesurfactants include, for example, ethoxylates of Adogen 560 (N-cocopropylene diamine) containing an average of from 2EO to 20EO, forexample, 4.8, 10 or 13.4EO; ethoxylates of Adogen 570 (N-tallowpropylene diamine) containing an average of form 2EO to 20EO, forexample, 13EO; and ethoxylates of Adogen 670 (N-tallow propylenetriamine) containing an average of from 3EO to 20EO, for example, 14.9EOall of which are available from Witco Corp.

Other polyamine surfactants for use in the herbicidal formulations ofthe present invention have the general structure (26):

wherein R₂₆₁ is C₈₋₂₀, R₂₆₂ is C₁₋₄ and n is 2 or 3. Examples ofpolyamines for use in the formulations and methods of the presentinvention include Triamine C(R₂₆₁ is coco (C₁₀₁₄)), R₂₆₂ is C₃, n is 2and amine number (total mg KOH/g) is 500-525), Triamine OV (R₂₆₁ isoleyl (vegetable oil), R₂₆₂ is C₃, n is 2 and amine number (total mgKOH/g) is 400-420), Triamine T (R₂₆₁ is tallow (C₁₆₋₁₈), R₂₆₂ is C₃, nis 2 and amine number (total mg KOH/g) is 415-440), Triamine YT (R₂₆₁ istallow (C₁₆₋₁₈), R₂₆₂ is C₃, n is 2 and amine number (total mg KOH/g) is390-415), Triameen Y12D (R₂₆₁ is dodecyl (C₁₂), R₂₆₂ is C₃, n is 2 andamine number (total mg HCl/g is 112-122), Triameen Y12D-30 (R₂₆₁ isdodecyl (C₁₂), R₂₆₂ is C₃, n is 2 and amine number (total mg HCl/g is335-365), Tetrameen OV (R₂₆₁ is oleyl (vegetable oil), R₂₆₂ is C₃, n is3 and amine number (total mg KOH/g) is 470-500), Tetrameen T (R₂₆₁ istallow (C₁₆₋₁₈), R₂₆₂ is C₃, n is 3 and amine number (total mg KOH/g) is470-495), wherein each is available from Akzo Nobel.

Sulfate surfactants for use in the herbicidal formulations of thepresent invention have the general structure (27a-c):

wherein compounds of formula (27a) are alkyl sulfates, compounds offormula (27b) are alkyl ether sulfates and compounds of formula (27c)are alkyl aryl ether sulfates. R₂₇₁ is a hydrocarbyl or substitutedhydrocarbyl having from about 4 to about 22 carbon atoms, each R₂₇₂ isindependently ethyl, isopropyl or n-propyl and n is from 1 to about 20.M is selected from an alkali metal cation, ammonium, an ammoniumcompound or H⁺. Examples of alkyl sulfates include sodium C₈₋₁₀ sulfate,sodium C₁₀₋₁₆ sulfate, sodium lauryl sulfate, sodium C₁₄₋₁₆ sulfate,diethanolamine lauryl sulfate, triethanolamine lauryl sulfate andammonium lauryl sulfate. Examples of alkyl ether sulfates include sodiumC₁₂₋₁₆ pareth sulfate (1 EO), ammonium C₆₋₁₀ alcohol ether sulfate (3EO), sodium C₆₋₁₀ alcohol ether sulfate (3 EO), isopropylammonium C₆₋₁₀alcohol ether sulfate (3 EO), ammonium C₁₀₋₁₂ alcohol ether sulfate (3EO), sodium lauryl ether sulfate (3 EO). Examples of alkyl aryl ethersulfates include sodium nonylphenol ethoxylate sulfate (4 EO), sodiumnonylphenol ethoxylate sulfate (10 EO), Witcolate™ 1247H (C₈₋₁₀, 3EO,ammonium sulfate), WITCOLATE 7093 (C₆₋₁₀, 3EO, sodium sulfate),WITCOLATE 7259 (C₈₋₁₀ sodium sulfate), WITCOLATE 1276 (C₁₀₋₁₂, 5EO,ammonium sulfate), WITCOLATE LES-60A (C₁₂₋₁₄, 3EO, ammonium sulfate),WITCOLATE LES-60C (C₁₂₋₁₄, 3EO, sodium sulfate), WITCOLATE 1050 (C₁₂₋₁₅,10EO, sodium sulfate), WITCOLATE WAQ (C₁₂₋₁₆ sodium sulfate), WITCOLATED-51-51 (nonylphenol 4EO, sodium sulfate) and WITCOLATE D-51-53(nonylphenol 10EO, sodium sulfate).

Sulfonate surfactants for use in the herbicidal formulations of thepresent invention correspond to sulfate structures (27a) through (27c)above except the R-substituted moiety is attached directly to the sulfuratom, for instance R₂₇₁503. Examples of sulfonate surfactants include,for example, Witconate™ 93S (isopropylamine of dodecylbenzenesulfonate), WITCONATE NAS-8 (octyl sulfonic acid, sodium salt),WITCONATE AOS (tetradecyl/hexadecyl sulfonic acid, sodium salt),WITCONATE 60T (linear dodecylbenzene sulfonic acid, triethanolaminesalt) and WITCONATE 605a (branched dodecylbenzene sulfonic acid,N-butylamine salt).

Phosphate esters of alkoxylated alcohol surfactants for use in theherbicidal formulations of the present invention have the generalmonoester structure (28a) and the general diester structure (28b):

wherein R₂₈₁ is a hydrocarbyl or substituted hydrocarbyl having fromabout 4 to about 22 carbon atoms; R₂₈₂ is a hydrocarbylene having 2, 3,or 4 carbon atoms; m is an average number from about 1 to about 60; andR₂₈₃ and R₂₈₄ are each independently hydrogen or a linear or branchedchain alkyl having from 1 to about 6 carbon atoms.

R₂₈₁ is preferably an alkyl having from about 4 to about 22 carbonatoms, more preferably from about 8 to about 20 carbon atoms, or analkylphenyl having from about 4 to about 22 carbon atoms, morepreferably from about 8 to about 20 carbon atoms. Sources of the R₂₈₁group include, for example, coco or tallow, or R₂₈₁ may be derived fromsynthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl,hexadecyl, or octadecyl groups. R₂₈₂ may be propylene, isopropylene, orethylene, and is preferably ethylene. m is preferably from about 9 toabout 15. R₂₈₃ and R₂₈₄ are preferably hydrogen.

Specific phosphate esters of alkoxylated alcohol surfactants for use inthe herbicidal formulation of the present invention include, forexample, EMPHOS CS-121, EMPHOS PS-400, and WITCONATE D-51-29, availablefrom Witco Corp. Other examples are indicated in table C below for thePhospholan produces (available from Akzo Nobel) wherein the surfactantsmay comprise a mixture of the monoester and diester forms and whereinR₂₈₄ is not present in the diester as indicated and “prop.” refers toproprietary and “NR” refers to not reported. In some embodiments, thephosphate esters of the general monoester structure (28a) and thegeneral diester structure (28b) are not alkoxylated, i.e., m is 0.Examples of commercial products include Phospholan PS-900 and Phospholan3EA.

TABLE C mono and Tradename R₂₈₁ R₂₈₂ R₂₈₃/R₂₈₄ m di forms Phospholannonyl phenol C₂ H 6 mono & di CS-131 Phospholan nonyl phenol C₂ H 6 highmono CS-1361 & di Phospholan nonyl phenol C₂ H 10  mono & di CS-141Phospholan nonyl phenol C₂ H 8 mono & di CS-147 Phospholan prop. prop.prop. prop. mono KPE4 Phospholan tridecyl C₂ H NR NR PS-131 Phospholandecyl/tetradecyl C₂ H 30  mono & di PS-220 Phospholan dodecyl/ C₂ H 3mono & di PS-222 pentadecyl Phospholan decyl/dodecyl C₂ H 7 mono & diPS-236 Phospholan tridecyl alcohol — H — mono & di PS-900 Phospholanphenyl C₂ H 7 mono & di TS-230 Phospholan triethanolamine — H — mono 3EAamine

Alkyl polysaccharide surfactants for use in the herbicidal formulationsof the present invention have the general structure (29):

R₂₉₁—O-(sug)_(u)  (29)

wherein R₂₉₁ is a straight or branched chain substituted orunsubstituted hydrocarbyl selected from alkyl, alkenyl, alkylphenyl,alkenylphenyl having from about 4 to about 22 carbon atoms, wherein sugand u are as defined above. In various particular embodiments thepolysaccharide surfactant may be an alkyl polyglucoside of formula (29)wherein: R₂₉₁ is a branched or straight chain alkyl group preferablyhaving from 4 to 22 carbon atoms, more preferably from 8 to 18 carbonatoms, or a mixture of alkyl groups having an average value within thegiven range; sug is a glucose residue; and u is between 1 and about 5,and more preferably between 1 and about 3.

Examples of surfactants of formula (29) are known in the art.Representative surfactants are presented in Table D below wherein foreach surfactant sug is a glucose residue.

TABLE D Trade name R₂₉₁ U APG 225 C₈₋₁₂ alkyl 1.7 APG 325 C₉₋₁₁ alkyl1.5 APG 425 C₈₋₁₆ alkyl 1.6 APG 625 C₁₂₋₁₆ alkyl 1.6 GLUCOPON 600 C₁₂₋₁₆alkyl 1.4 PLANTAREN 600 C₁₂₋₁₄ alkyl 1.3 PLANTAREN 1200 C₁₂₋₁₆ alkyl 1.4PLANTAREN 1300 C₁₂₋₁₆ alkyl 1.6 PLANTAREN 2000 C₈₋₁₆ alkyl 1.4 AgrimulPG 2076 C₈₋₁₀ alkyl 1.5 (synonymous with AGNIQUE PG 8105) Agrimul PG2067 C₈₋₁₀ alkyl 1.7 (synonymous with AGNIQUE PG 8107) Agrimul PG 2072C₈₋₁₆ alkyl 1.6 (synonymous with AGNIQUE PG 816) Agrimul PG 2069 C₉₋₁₁alkyl 1.6 (synonymous with AGNIQUE PG 9116) Agrimul PG 2062 C₁₂₋₁₆ alkyl1.4 (synonymous with AGNIQUE PG 264) Agrimul PG 2065 C₁₂₋₁₆ alkyl 1.6(synonymous with AGNIQUE PG 266) BEROL AG6202 2-ethyl-1-hexyl

Alkoxylated alcohol surfactants for use in the herbicidal formulationsof the present invention have the general structure (30):

R₃₀₁O—(R₃₀₂O)_(x)R₃₀₃  (30)

wherein R₃₀₁ is hydrocarbyl or substituted hydrocarbyl having from 1 toabout 30 carbon atoms, R₃₀₂ in each of the (R₃₀₂O)_(x) groups isindependently C₂-C₄ alkylene, R₃₀₃ is hydrogen, or a linear or branchedalkyl group having from 1 to about 4 carbon atoms, and x is an averagenumber from 1 to about 60. In this context, preferred R₃₀₁ hydrocarbylgroups are linear or branched alkyl, linear or branched alkenyl, linearor branched alkynyl, aryl, or aralkyl groups. Preferably, R₃₀₁ is alinear or branched alkyl or linear or branched alkenyl group having fromabout 8 to about 30 carbon atoms, R₃₀₂ in each of the (R₃₀₂O)_(x) groupsis independently C₂-C₄ alkylene, R₃₀₃ is hydrogen, methyl or ethyl, andx is an average number from about 5 to about 50. More preferably, R₃₀₁is a linear or branched alkyl group having from about 8 to about 25carbon atoms, R₃₀₂ in each of the (R₃₀₂O)_(x) groups is independentlyethylene or propylene, R₃₀₃ is hydrogen or methyl, and x is an averagenumber from about 8 to about 40. Even more preferably, R₃₀₁ is a linearor branched alkyl group having from about 12 to about 22 carbon atoms,R₃₀₂ in each of the (R₃₀₂O)_(x) groups is independently ethylene orpropylene, R₃₀₃ is hydrogen or methyl, and x is an average number fromabout 8 to about 30. Preferred commercially available alkoxylatedalcohols include: Emulgin™ L, Procol™ LA-15 (from Protameen); Brij™ 35,Brij™ 56, Brij™ 76, Brij™ 78, Brij™ 97, Brij™ 98 and Tergitol™ XD (fromSigma Chemical Co.); Neodol™ 25-12 and Neodol™ 45-13 (from Shell);Hetoxol™ CA-10, Hetoxol™ CA-20, Hetoxol™ CS-9, Hetoxol™ CS-15, Hetoxol™CS-20, Hetoxol™ CS-25, Hetoxol™ CS-30, Plurafac™ A38 and Plurafac™ LF700(from BASF); ST-8303 (from Cognis); Arosurf™ 66E10 and Arosurf™ 66E20(from Witco/Crompton); ethoxylated (9.4 EO) tallow, propoxylated (4.4EO) tallow and alkoxylated (5-16 EO and 2-5 PO) tallow (fromWitco/Crompton). Also preferred are; SURFONIC™ NP95 of Huntsman (apolyoxyethylene (9.5) nonylphenol); TERGITOL series from Dow andcommercially available from Sigma-Aldrich Co. (Saint Louis, Mo.),including TERGITOL-15-S-5, TERGITOL-15-S-9, TERGITOL-15-S-12 andTERGITOL-15-S-15 (made from secondary, linear C₁₁ to C₁₅ alcohols withan average of 5 moles, 9 moles, 12.3 moles and 15.5 moles ofethoxylation, respectively); the SURFONIC LF-X series from HuntsmanChemical Co. (Salt Lake City, Utah), including L12-7 and L12-8 (madefrom linear C₁₀ to C₁₂ alcohols with an average of 7 moles and 8 moles,respectively, of ethoxylation), L24-7, L24-9 and L24-12 (made fromlinear C₁₂ to C₁₄ alcohols with an average of 7 moles, 9 moles and 12moles of ethoxylation, respectively), L68-20 (made from primary, linearC₁₆₋₁₈ alcohols with an average of 20 moles of ethoxylation) and L26-6.5(made from linear C₁₂ to C₁₆ alcohols with an average of 6.5 moles ofethoxylation); and Ethylan 68-30 (C₁₆₋₁₈ with an average of 20 moles ofethoxylation) available from Akzo Nobel.

In some embodiments of the present invention, the surfactant is selectedfrom alkoxylated tertiary etheramines, alkoxylated quaternaryetheramines, alkoxylated etheramine oxides, alkoxylated tertiary amines,alkoxylated quaternary amines, alkoxylated polyamines, sulfates,sulfonates, phosphate esters, alkyl polysaccharides, alkoxylatedalcohols, and combinations thereof.

In some other embodiments, amidoalkylamine surfactants can optionally beformulated in compositions of the present invention comprisingglyphosate co-herbicide. Amidoalkylamine surfactants for use in suchherbicidal formulations of the present invention have the generalstructure (31):

wherein R₃₁₁ is a hydrocarbyl or substituted hydrocarbyl having from 1to about 22 carbon atoms, R₃₁₂ and R₃₁₃ are each independentlyhydrocarbyl or substituted hydrocarbyl having from 1 to about 6 carbonatoms and R₃₁₄ is hydrocarbylene or substituted hydrocarbylene havingfrom 1 to about 6 carbon atoms.

R₃₁₁ is preferably an alkyl or substituted alkyl having an average valueof carbon atoms between about 4 to about 20 carbon atoms, preferably anaverage value between about 4 and about 18 carbon atoms, more preferablyan average value from about 4 to about 12 carbon atoms, more preferablyan average value from about 5 to about 12 carbon atoms, even morepreferably an average value from about 6 to about 12 carbon atoms, andstill more preferably an average value from about 6 to about 10 carbonatoms. The R₃₁₁ alkyl group may be derived from a variety of sourcesthat provide alkyl groups having from about 4 to about 18 carbon atoms,for example, the source may be butyric acid, valeric acid, caprylicacid, capric acid, coco (comprising mainly lauric acid), myristic acid(from, e.g., palm oil), soy (comprising mainly linoleic acid, oleicacid, and palm itic acid), or tallow (comprising mainly palm itic acid,oleic acid, and stearic acid). In some embodiments, the amidoalkylaminesurfactant component may comprise a blend of amidoalkylamines havingalkyl chains of various lengths from about 5 carbon atoms to about 12carbon atoms. For example, depending upon the source of the R₃₁₁ alkylgroup, an amidoalkylamine surfactant component may comprise a blend ofsurfactants having R₃₁₁ groups that are 5 carbon atoms in length, 6carbon atoms in length, 7 carbon atoms in length, 8 carbon atoms inlength, 9 carbon atoms in length, 10 carbon atoms in length, 11 carbonatoms in length, and 12 carbon atoms in length, longer carbon chains,and combinations thereof. In other embodiments, the amidoalkylaminesurfactant component may comprise a blend of surfactants having R₃₁₁groups that are 5 carbon atoms in length, 6 carbon atoms in length, 7carbon atoms in length, and 8 carbon atoms in length. In somealternative embodiments, the amidoalkylamine surfactant component maycomprise a blend of surfactants having R₁ groups that are 6 carbon atomsin length, 7 carbon atoms in length, 8 carbon atoms in length, 9 carbonatoms in length, and 10 carbon atoms in length. In other embodiments,the amidoalkylamine surfactant component may comprise a blend ofsurfactants having R₃₁₁ groups that are 8 carbon atoms in length, 9carbon atoms in length, 10 carbon atoms in length, 11 carbon atoms inlength, and 12 carbon atoms in length.

R₃₁₂ and R₃₁₃ are independently preferably an alkyl or substituted alkylhaving from 1 to about 4 carbon atoms. R₃₁₂ and R₃₁₃ are most preferablyindependently an alkyl having from 1 to about 4 carbon atoms, and mostpreferably methyl. R₃₁₄ is preferably an alkylene or substitutedalkylene having from 1 to about 4 carbon atoms. R₃₁₄ is most preferablyan alkylene having from 1 to about 4 carbon atoms, and most preferablyn-propylene. When R₃₁₄ is n-propylene, the amidoalkylamine surfactantsare termed amidopropylamine (APA) surfactants.

In one preferred amidoalkylamine surfactant, R₃₁₁ is C₆₋₁₀, i.e., analkyl group having 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9carbon atoms, 10 carbon atoms, or a blend of any of these, i.e., fromabout 6 carbon atoms to about 10 carbon atoms; R₃₁₂ and R₃₁₃ are eachmethyl; and R₃₁₄ is n-propylene (i.e., C₆₋₁₀ amidopropyl dimethylamine).

Examples of APA surfactants include Armeen APA 2 (where R₃₁₁ is C₂ andR₃₁₂ and R₃₁₃ are each hydrogen), Armeen APA 6 (where R₃₁₁ is C₆ andR₃₁₂ and R₃₁₃ are each methyl), Armeen APA 8, 10 (where R₃₁₁ is C₈₋₁₀and R₃₁₂ and R₃₁₃ are each methyl), Armeen APA 12 (where R₃₁₁ is C₁₂ andR₃₁₂ and R₃₁₃ are each methyl), ACAR 7051 (where R₃₁₁ is C₆₋₉ and R₃₁₂and R₃₁₃ are each methyl), ACAR 7059 (where R₃₁₁ is 2-ethyl hexyl andR₃₁₂ and R₃₁₃ are each methyl) and Adsee C80W (where R₃₁₁ is Coco andR₃₁₂ and R₃₁₃ are each methyl).

In some embodiments of the present invention, certain polybasic aminepolymers may precipitate from solution in acidic aqueous formulations.It has been discovered that certain solubilizers improve amine polymersolubility in such formulations and function to prevent or inhibitprecipitation. Under one theory, and without being bound to anyparticular theory, it is believed that the solubilizers help to maintainamine site hydration thereby inhibiting collapse of the polymerthree-dimensional structure and associated precipitation from solution.It has been discovered that amine surfactants can function as bothherbicidal efficacy enhancers and solubilizers. Such solubilizersinclude, for example, amine surfactants such as alkoxylated tertiaryetheramines, alkoxylated quaternary etheramines, alkoxylated etheramineoxides, alkoxylated tertiary amine oxides, alkoxylated tertiary amines,alkoxylated quaternary amines, polyamines, alkoxylated polyamines andbetaines. Solubilizers may also include primary, secondary or tertiaryC₄ to C₁₆ alkyl or aryl amine compounds, or the corresponding quaternaryammonium compounds. A weight ratio of polymer to solubilizer of fromabout 1:1 to about 50:1 is preferred, more preferably from about 2:1 toabout 25:1.

In one embodiment, compounds which enhance polymer solubility includeamines or quaternary ammonium salt compounds having the generalstructures (32) and (33)

wherein R₃₂₀ is linear or branched alkyl or aryl having from about 4 toabout 16 carbon atoms, R₃₂₁ is hydrogen, methyl or ethyl, R₃₂₂ ishydrogen, methyl or ethyl; R₃₂₃ is hydrogen or methyl; and A⁻ is anagriculturally acceptable anion. Non-limiting examples include, mixedC₈₋₁₆ alkyl amine (Armeen C), dimethylcocoamine (Arquad DMCD),cocoammonium chloride (Arquad C), of which are manufactured by AkzoNobel, hexylamine, dimethylhexylamine, octylamine, dimethyloctylamine,dodecyltrimethyl amide and C₄₋₈ trialkyl amines.

In some embodiments of the present invention, amidoalkylaminesurfactants, as described above, can optionally be formulated as asolubilizer in compositions of the present invention comprisingglyphosate co-herbicide.

Alkoxylated tertiary etheramines, alkoxylated quaternary etheramines,alkoxylated tertiary amines, alkoxylated quaternary amines, andoctylamines are generally preferred stabilizers and, based onexperimental evidence to date, provide greater polymer solubility andstability on a weight ratio basis than do amidoalkylamines.

The formulations of the invention may further comprise other additivessuch as conventional drift control agents, safeners, thickeners, flowenhancers, antifoaming agents, freeze protectants and/or UV protectants.Suitable drift control agents are known to those skilled in the art andinclude the commercial products Gardian®, Gardian Plus®, Dri-Gard®,Pro-One XL™, Array™, Compadre™, In-Place®, Bronc® Max EDT, EDTConcentrate™, Coverage® and Bronc® Plus Dry EDT. Safeners are likewiseknown to those skilled in the art and include isoxadifen, benoxacor anddichlormid.

In some embodiments of the present invention, the dicamba formulationsof the present invention are used in the preparation of concentrate,tank mix or ready to use (RTU) formulations further comprising one ormore additional co-herbicides. Co-herbicides include auxin herbicidesalts other than dicamba salts (as previously described). Co-herbicidesalso include acetyl CoA carboxylase (ACCase) inhibitors, acetolactatesynthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors,photosystem II inhibitors, photosystem I inhibitors, protoporphyrinogenoxidase (PPO or Protox) inhibitors, carotenoid biosynthesis inhibitors,enolpyruvyl shikimate-3-phosphate (EPSP) synthase inhibitor, glutaminesynthetase inhibitor, dihydropteroate synthetase inhibitor, mitosisinhibitors, synthetic auxins, auxin transport inhibitors and nucleicacid inhibitors, salts and esters thereof, and combinations thereof.

Included within the scope of co-herbicides are racemic mixtures andresolved isomers. Typical cations for the co-herbicide salts of thepresent invention include potassium, MEA, DMA, IPA, trimethylsulfonium(TMS) diethylammonium (DEA), lithium, and ammonium. Typical anions forthe formation of co-herbicide salts include chlorine, bromine, fluorineand acetate. Typical esters include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, pentyl, isooctyl, ethylhexyl, ethoxyethyl, butoxyethyl,butoxypropyl and octanoate.

Examples of ACCase inhibitors include clethodim, clodinafop,fenoxaprop-P, fluazifop-P, quizalofop-P and sethoxydim. Examples of ALSor AHAS inhibitors include flumetsulam, imazamethabenz-m, imazamox,imazapic, imazapyr, imazaquin, imazethapyr, metsulfuron, prosulfuron andsulfosulfuron. Examples of photosystem I inhibitors include diquat andparaquat. Examples of photosystem II inhibitors include atrazine,cyanazine and diuron. Examples of PPO inhibitors include acifluorofen,butafenacil, carfentrazone-ethyl, flufenpyr-ethyl, fluthiacet,flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyflurofenand sulfentrazone. Examples of carotenoid biosynthesis inhibitorsinclude aclonifen, amitrole, diflufenican and sulcotrione. Glyphosate isan EPSP inhibitor, glufosinate is a glutamine synthetase inhibitor andasulam is a dihydropteroate synthetase inhibitor. Examples of mitosisinhibitors include acetochlor, alachlor, dithiopyr, S-metolachlor andthiazopyr. Naptalam is an example of a auxin transport inhibitor.Examples of nucleic acid inhibitors include difenzoquat, fosamine,metham and pelargonic acid.

Examples of suitable water-soluble herbicides include, withoutrestriction, 2,4-D, aminopyralid, clopyralid, fluroxypyr, MCPA, andsalts thereof; 2,4-DB salts, dichlorprop salts, MCPB salts, mecopropsalts, picloram salts, quinclorac salts, and triclopyr salts; and watersoluble acids, salts and esters of acifluorfen, alloxydim, aminocarbazone, am idosulfuron, am itrole, asulam, azafenidin,azimsulfuron, beflubutamid, benazolin, bentazon, bensulfuron-methyl,bispyribac, bromacil, carbetamide, carfentrazone-ethyl,chlorimuron-ethyl, chlorsulfuron, cinosulfuron, clomazone, dalapon,dazomet, dicamba, dichlormid, diclofop, diclopyr, difenzoquat,deflufenzopyr, dimethachlor, dimethenamid, dimethipin, diquat dibromide,DNOC, DSMA, endothall, exasulfuron, flazasulfuron, floramsulfuron,florasulam, flucarbazone-sodium, flupropanate, fluthiacet, fomesafen,foramsulfuron, fosamine, glyphosate, glufosinate, glufosinate-P,hexazinone, imazamethabenz-methyl, imazamox, imazapic-ammonium,imazapyr, imazaquin-ammonium, imazethapyr-ammonium, iodosulfuron,mesotrione, metam, metamitron, metham, metosulam, metribuzin,metsulfuron-methyl, molinate, monolinuron, MSMA, water soluble salts ofoleic acid, naptalam, oxasulfuron, paraquat dichloride, water-solublesalts of pelargonic acid, penoxsulam, prometon, propoxycarbazone-sodium,prosulfuron, pyrithiobac-sodium, quinmerac, rimsulfuron, sethoxydim,sulfosulfuron, TBA, tebuthiuron, terbacil, thifensulfuron-methyl,tralkoxydim, triasulfuron, tribenuron-methyl, triclopyr, andtrifloxysulfuron; racemic mixtures and resolved isomers thereof; andmixtures thereof.

Examples of suitable water-insoluble herbicides include, withoutrestriction, acetochlor, acifluorfen, aclonifen, alachlor, ametryn,anilofos, atrazine, azafenidin, benfluralin, bensulfuron-methyl,bensulide, benzofenap, bifenox, bromoxynil, butachlor, butroxydim,butylate, cafenstrole, chlomethoxyfen, chlorbromuron, chloridazon,chlornitrofen, chlorotoluron, chlorthal-dimethyl, chlorthiamid,cinmethylin, clethodim, clodinafop-propargyl, cloransulam-methyl,cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl,desmedipham, desmetryn, dichlobenil, diclosulam, diflufenican,dimefuron, dimepiperate, dimethachlor, dinitramine, dinoterb, dithiopyr,diuron, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl,ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fentrazamide,fluazifop-butyl, flucetosulfuron, fluchloralin, flufenacet,flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin,fluometuron, fluorochloridone, fluoroglycofen,flupyrsulfuron-methyl-sodium, fluridone, fluroxypyr-1-methylheptyl,flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, furyloxyfen,halosulfuron-methyl, haloxyfop-methyl, imazosulfuron, ioxynil,isoproturon, isoxaben, isoxaflutole, lactofen, lenacil, linuron,mefenacet, metazachlor, methabenzthiazuron, metobromuron, metolachlor,metosulam, metoxuron, metribuzin, molinate, monolinuron, napropamide,niocosulfuron, nitrofen, nitrofluorfen, norflurazon, oryzalin,oxadiargyl, oxadiazon, oxasulfuron, oxyfluorfen, pebulate, pelargonicacid, pendimethalin, phenmedipham, pretilachlor, primisulfuron-methyl,prodiamine, prometon, prometryn, propachlor, propanil, propaquizafop,propisochlor, propyzamide, prosulfocarb, pyraflufen-ethyl, pyrazolynate,pyrazon, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenoxim, pyridate,quinclorac, quinmerac, quizalofop-ethyl, rimsulfuron, siduron, simazine,simetryn, sulcotrione, sulfentrazone, sulfometuron, terbacil,terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr,thiobencarb, triallate, trietazine, trifluralin, triflusulfuron-methyl,and vernolate, agriculturally acceptable salts or esters of any of theseherbicides, racemic mixtures and resolved isomers thereof, andcombinations thereof.

Some preferred water-soluble herbicides include 2,4-D and salts thereof,acifluorfen salts, carfentrazone-ethyl, fomesafen salts, glyphosate andsalts thereof, glufosinate and salts thereof, imazamethabenz and saltsand esters thereof, imazamox and salts and esters thereof, imazapic andsalts and esters thereof, imazapyr and salts and esters thereof,imazaquin and salts and esters thereof, imazethapyr and salts and estersthereof, mecoprop salts, triclopyr salts, racemic mixtures and resolvedisomers thereof, and combinations thereof. Some preferredwater-insoluble herbicides include acetochlor, alachlor, atrazine,azafenidin, bifenox, butachlor, butafenacil, diuron, dithiopyr,flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen,fluthiacet-methyl, lactofen, metazochlor, metolachlor (andS-metolachlor), oxadiargyl, oxadiazon, oxyfluorfen, pretilachlor,propachlor, propisochlor, pyraflufen-ethyl, sulfentrazone andthenylchlor, racemic mixtures and resolved isomers thereof, andcombinations thereof.

Tank mix and RTU co-herbicide formulations of the present inventiontypically comprise from about 0.1 g a.e./L to about 50 g a.e./L totalherbicide loading while co-herbicide concentrate formulations of thepresent invention typically comprise from about 50 to about 750 ga.e./L, from about 300 to about 750 g a.e./L, from about 350 to about ga.e./L, from about 400 to about 750 g a.e./L, from about 450 to about750 g a.e./L, or even from about 500 to about 750 g a.e./L. For example,50, 51, 55, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 577.5,600, 650, 700, or even 750 g a.e./L, and ranges thereof. In co-herbicideformulations, a weight ratio on an acid equivalent basis of the auxinherbicide to the total co-herbicide of no greater than about 50:1, forexample, about 50:1, 25:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5 oreven about 1:10 and ranges thereof, for example, from about 50:1 toabout 1:10, from about 50:1 to about 1:5, from about 50:1 to about 1:1,from about 50:1 to about 3:1, from about 50:1 to about 5:1, from about50:1 to about 10:1, from about 25:1 to about 1:1, or from about 25:1 toabout 3:1, are preferred. For any given auxin herbicide andconcentration thereof, one skilled in the art can readily determineusing routine experimentation a minimum ratio of that auxin herbicide toany co-herbicide or combination of co-herbicides that is necessary toachieve the objects of the invention in view of the other components ofthe formulation, such as a polybasic polymer component and/or surfactantcomponent and their respective concentrations.

In some embodiments of the present invention, an auxin herbicide (e.g.,dicamba) is combined with a co-herbicide selected from glyphosate,glufosinate (or glufosinate-P), an ALS inhibitor, salts and estersthereof, or combinations thereof, for application to transgenic plantscomprising an auxin (e.g., dicamba, 2,4-D or fluroxypyr) resistanttrait, a glyphosate resistant trait, a glufosinate resistant trait, anALS resistant trait, or combinations thereof.

Crop tolerance to specific herbicides can be conferred by engineeringgenes into crops which encode appropriate herbicide metabolizing enzymesand/or insensitive herbicide targets. Technology for introduction of aDNA molecule (genes) into cells is well known to those of skill in theart. Methods and materials for transforming plant cells by introducing aDNA construct into a plant genome in the practice of this invention caninclude any of the well-known and demonstrated methods including, butnot limited to:

(1) chemical methods (Graham and Van der Eb, Virology, 54(2):536-539(1973) and Zatloukal, et al., Ann. N. Y. Acad. Sci., 660: 136-153(1992));

(2) physical methods such as microinjection (Capecchi, Cell,22(2):479-488 (1980)), electroporation (Wong and Neumann, Biochim.Biophys. Res. Commun., 107(2):584-587 (1982); Fromm, et al, Proc. Natl.Acad. Sci. USA, 82(17):5824-5828 (1985); U.S. Pat. No. 5,384,253)particle acceleration (Johnston and Tang, Methods Cell Biol.,43(A):353-365 (1994); Fynan, et al., Proc. Natl. Acad. Sci. USA,90(24):11478-11482 (1993)): and microprojectile bombardment (asillustrated in U.S. Pat. Nos. 5,015,580; 5,550,318; 5,538,880;6,160,208; 6,399,861; and 6,403,865);

(3) viral vectors (Clapp, Clin. Perinatol., 20(1):155-168 (1993); Lu, etal., J. Exp. Med., 178(6):2089-2096 (1993); Eglitis and Anderson,Biotechniques, 6(7):608-614 (1988));

(4) receptor-mediated mechanisms (Curiel et al., Hum. Gen. Ther.,3(2):147-154 (1992) and Wagner, et al., Proc. Natl. Acad. Sci. USA,89(13):6099-6103 (1992);

(5) bacterial mediated mechanisms such as Agrobacterium-mediatedtransformation (as illustrated in U.S. Pat. Nos. 5,824,877; 5,591,616;5,981,840; and 6,384,301); direct introduction into pollen by injectinga plant's reproductive organs (Zhou, et al., Methods in Enzymology,101:433, (1983);

(6) Hess, Intern Rev. Cytol., 107:367 (1987); Luo, et al., Plant MolBiol. Reporter, 6:165 (1988); Pena, et al., Nature, 325:274 (1987));

(7) protoplast transformation (as illustrated in U.S. Pat. No.5,508,184); and

(8) injection into immature embryos (Neuhaus, et al., Theor. Appl.Genet., 75:30 (1987)).

Any of the above described methods may be utilized to transform a plantcell.

Methods for transforming dicotyledonous plants, primarily by use ofAgrobacterium tumefaciens and obtaining transgenic plants have beenpublished for cotton (U.S. Pat. Nos. 5,004,863; 5,159,135; and5,518,908); soybean (U.S. Pat. Nos. 5,569,834 and 5,416,011; see also,McCabe, et al., Biotechnolgy, 6:923 (1988) and Christou et al., PlantPhysiol. 87:671-674 (1988)); Brassica (U.S. Pat. No. 5,463,174); peanut(Cheng et al., Plant Cell Rep., 15:653-657 (1996) and McKently et al.,Plant Cell Rep., 14:699-703 (1995)); papaya; and pea (Grant et al.,Plant Cell Rep., 15:254-258 (1995)).

Transformations of monocotyledon plants using electroporation, particlebombardment, and Agrobacterium have also been reported. Transformationand plant regeneration have been achieved in asparagus (Bytebier, etal., Proc. Natl. Acad. Sci. (USA), 84:5354 (1987); barley (Wan andLemaux, Plant Physiol, 104:37 (1994)); maize (Rhodes, et al., Science240:204 (1988), Gordon-Kamm, et al., Plant Cell, 2:603-618 (1990),Fromm, et al., Bio/Technology, 8:833 (1990), Koziel et al.,Bio/Technology, 11:194 (1993), and Armstrong, et al., Crop Science,35:550-557 (1995)); oat (Somers, et al., Bio/Technology, 10:1589(1992)); orchard grass (Horn, et al., Plant Cell Rep.. 7:469 (1988));rye (De la Pena, et al., Nature, 325:274 (1987)); sugarcane (Bower andBirch, Plant Journal, 2:409 (1992)); tall fescue (Wang, et al.,Bio/Technology, 10:691 (1992)); and wheat (Vasil, et al.,Bio/Technology, 10:667 (1992) and U.S. Pat. No. 5,631,152).

The regeneration, development, and cultivation of plants fromtransformed plant protoplast or explants is well known in the art (see,for example, Weissbach and Weissbach, Methods for Plant MolecularBiology, (Eds.), Academic Press, Inc., San Diego, Calif. (1988) andHorsch et al., Science, 227:1229-1231 (1985)). Transformed cells aregenerally cultured in the presence of a selective media, which selectsfor the successfully transformed cells and induces the regeneration ofplant shoots and roots into intact plants (Fraley, et al., Proc. Natl.Acad. Sci. U.S.A., 80: 4803 (1983)). Transformed plants are typicallyobtained within two to four months.

The regenerated transgenic plants are self-pollinated to providehomozygous transgenic plants. Alternatively, pollen obtained from theregenerated transgenic plants may be crossed with non-transgenic plants,preferably inbred lines of agronomically important species. Descriptionsof breeding methods that are commonly used for different traits andcrops can be found in one of several reference books, see, for example,Allard, Principles of Plant Breeding, John Wiley & Sons, NY, U. of CA,Davis, Calif., 50-98 (1960); Simmonds, Principles of crop improvement,Longman, Inc., NY, 369-399 (1979); Sneep and Hendriksen, Plant breedingperspectives, Wageningen (ed), Center for Agricultural Publishing andDocumentation (1979); Fehr, Soybeans: Improvement, Production and Uses,2nd Edition, Monograph., 16:249 (1987); Fehr, Principles of varietydevelopment, Theory and Technique, (Vol 1) and Crop Species Soybean (Vol2), Iowa State Univ., Macmillian Pub. Co., NY, 360-376 (1987).Conversely, pollen from non-transgenic plants may be used to pollinatethe regenerated transgenic plants.

The transformed plants may be analyzed for the presence of the genes ofinterest and the expression level and/or profile conferred by theregulatory elements of the present invention. Those of skill in the artare aware of the numerous methods available for the analysis oftransformed plants. For example, methods for plant analysis include, butare not limited to Southern blots or northern blots, PCR-basedapproaches, biochemical analyses, phenotypic screening methods, fieldevaluations, and immunodiagnostic assays. The expression of atranscribable polynucleotide molecule can be measured using TaqMan®(Applied Biosystems, Foster City, Calif.) reagents and methods asdescribed by the manufacturer and PCR cycle times determined using theTaqMan® Testing Matrix. Alternatively, the Invader® (Third WaveTechnologies, Madison, Wis.) reagents and methods as described by themanufacturer can be used transgene expression.

The seeds of the plants of this invention can be harvested from fertiletransgenic plants and be used to grow progeny generations of transformedplants of this invention including hybrid plant lines comprising theconstruct of this invention and expressing a gene of agronomic interest.

Genetically engineered crop plants of the present include, for example,cotton, soybeans, sugar beet, sugar cane, plantation crops, tobacco,rape, maize and rice. Examples of crops having herbicidal resistancegiven by a genetic engineering technique include corn, soybean andcotton having resistance to glyphosate (Roundup Ready®) and glufosinate(Liberty Link®). Other examples of herbicide resistant crop plantsinclude dicamba, 2,4-D, dicamba or sethoxydim resistant corn, cotton andsoybean; imidazolinone (imazethapyr and imazapyr) resistant corn(Imi-Corn®) and soybeans; and glyphosate and glufosinate resistant corn(SmartStax®).

In some embodiments of the present invention, dicamba (or a saltthereof) is combined with glyphosate co-herbicide (or a salt or esterthereof), the crop plant comprises a glyphosate-resistant trait and thecrop plant is further either (i) a plant species not susceptible toauxin herbicides or (ii) comprises a dicamba resistant trait. Suchcompositions are useful to control (i) glyphosate susceptible plants and(ii) glyphosate resistant, but auxin susceptible, volunteer crop plantsand/or weeds growing in a field of (iii) glyphosate and auxin resistantor tolerant crop plants.

In some other embodiments of the present invention, the auxinco-herbicide is an ALS-inhibitor herbicide (or a salt or ester thereof),the crop plant comprises an ALS-resistant trait and the crop plant isfurther either (i) a plant species not susceptible to auxin herbicidesor (ii) comprises a dicamba resistant trait. Such compositions areuseful to control (i) ALS susceptible plants and (ii) ALS resistant, butauxin susceptible, volunteer crop plants and/or weeds growing in a fieldof (iii) ALS and auxin resistant or tolerant crop plants. Some preferredALS herbicides include am idosulfuron, azimsulfuron, florasulam,halosulfuron (-methyl), imazamethabenz, imazamox, imazapic, imazapyr,imazaquin, imazethapyr, imazosulfuron, iodosulfuron, metsulfuron(-methyl), nicosulfuron, primisulfuron (-methyl), prosulfuron,rimsulfuron, sulfosulfuron, thifensulfuron (-methyl), triasulfuron,tribenuron (-methyl), trifloxysulfuron and triflusulfuron (-methyl),salts and esters thereof, and racemic mixtures and resolved isomersthereof.

In some other embodiments of the present invention, the auxinco-herbicide is glufosinate (or glufosinate-P) (or a salt or esterthereof), the crop plant comprises a glufosinate-resistant trait and thecrop plant is further either (i) a plant species not susceptible toauxin herbicides or (ii) comprises a dicamba resistant trait. Suchcompositions are useful to control (i) glufosinate susceptible plantsand (ii) glufosinate resistant, but auxin susceptible, volunteer cropplants and/or weeds growing in a field of (iii) glufosinate and auxinresistant or tolerant crop plants.

In yet other embodiments of the present invention, glyphosate andglufosinate (or glufosinate-P) co-herbicides (or salts or estersthereof) are combined with an auxin herbicide, the crop plant is aspecies that comprises a glyphosate-resistant trait and aglufosinate-resistant trait, and the crop plant is further either (i) aplant species not susceptible to auxin herbicides or (ii) comprises adicamba resistant trait.

In still other embodiments embodiments of the present invention,glyphosate and at least one ALS inhibitor herbicide (or salts or estersthereof) are combined with an auxin herbicide, the crop plant is aspecies that comprises a glyphosate-resistant trait and an ALS-resistanttrait, and the crop plant is further either (i) a plant species notsusceptible to auxin herbicides or (ii) comprises a dicamba resistanttrait.

In yet other embodiments of the present invention, glufosinate (orglufosinate-P) and at least one ALS inhibitor herbicide (or salts oresters thereof) are combined with an auxin herbicide, the crop plant isa species that comprises a glufosinate-resistant trait and anALS-resistant trait, and the crop plant is further either (i) a plantspecies not susceptible to auxin herbicides or (ii) comprises a dicambaresistant trait.

In still other embodiments of the present invention, glyphosate,glufosinate (or glufosinate-P) and ALS inhibitor co-herbicides (or saltsor esters thereof) are combined with an auxin herbicide (e.g., dicamba)and the crop plant possesses glyphosate, glufosinate and ALS resistanttraits and the crop plant is further either (i) a plant species notsusceptible to auxin herbicides or (ii) comprises a dicamba resistanttrait.

In herbicidal methods of the present invention of using a formulation ofthe invention, an application mixture, typically comprising from about0.1 to about 50 g a.e./L herbicide, is formed and then applied to thefoliage of a plant or plants at an application rate sufficient to give acommercially acceptable rate of weed control. Application mixtures aretypically prepared from aqueous concentrate formulations by dilutionwith water to achieve the desired concentration. This application rateis usually expressed as amount of auxin herbicide per unit area treated,e.g., grams acid equivalent per hectare (g a.e./ha). Depending on plantspecies and growing conditions, the period of time required to achieve acommercially acceptable rate of weed control can be as short as a weekor as long as three weeks, four weeks or 30 days. Typically a period ofabout two to three weeks is needed for the auxin herbicide to exert itsfull effect.

The formulations of the present invention can be applied pre-planting ofthe crop plant, such as from about 2 to about 3 weeks before plantingauxin-susceptible crop plants or crop plants not having adicamba-resistant trait. Crop plants that are not susceptible to certainauxin herbicides, such as corn, or plants having the dicamba-resistanttrait typically have no pre-planting restriction and the formulations ofthe present invention can be applied immediately before planting suchcrops.

The formulations of the present invention can be applied at planting orpost-emergence to crop plants having a dicamba-resistant trait tocontrol auxin-susceptible weeds in a field of the crop plants and/oradjacent to a field of the crop plants. The formulations of the presentinvention can also be applied post-emergence to crop plants and/oradjacent to crop plants not having a dicamba resistant trait, such ascorn, but that are not susceptible to auxin herbicides.

When a maximum or minimum “average number” is recited herein withreference to a structural feature such as oxyethylene units of asurfactant, or molecular weight or nitrogen content of a polybasicpolymer, it will be understood by those skilled in the art that theinteger number of such units in individual molecules typically variesover a range that can include integer numbers greater than the maximumor smaller than the minimum “average number”. The presence in aformulation of individual molecules having an integer number of suchunits outside the stated range in “average number” does not remove theformulation from the scope of the present invention, so long as the“average number” is within the stated range and other requirements aremet.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

EXAMPLES

The following non-limiting examples are provided to further illustratethe present invention.

The herbicidal effectiveness data set forth herein report “inhibition”as a percentage following a standard procedure in the art which reflectsa visual assessment of plant mortality and growth reduction bycomparison with untreated plants, made by technicians specially trainedto make and record such observations. In all cases, a single technicianmakes all assessments of percent inhibition within any one experiment ortrial. Such measurements are relied upon and regularly reported byMonsanto Technology LLC in the course of its herbicide business.

The selection of application rates that are biologically effective for aspecific auxin herbicide is within the skill of the ordinaryagricultural scientist. Those of skill in the art will likewiserecognize that individual plant conditions, weather and growingconditions, as well as the specific exogenous chemical and formulationthereof selected, will affect the weed efficacy and associated cropinjury achieved in practicing this invention. Useful application ratesfor the auxin herbicides employed can depend upon all of the aboveconditions. With respect to the use of the method of this invention,much information is known about appropriate auxin application rates, anda weed control practitioner can select auxin application rates that areherbicidally effective on particular species at particular growth stagesin particular environmental conditions.

Effectiveness in greenhouse tests, usually at exogenous chemical rateslower than those normally effective in the field, is a proven indicatorof consistency of field performance at normal use rates. As illustratedin the Examples herein, a pattern of enhancement emerges over a seriesof greenhouse tests; when such a pattern is identified this is strongevidence of biological enhancement that will be useful in the field.

The formulations of the present invention can be applied to plants byspraying, using any conventional means for spraying liquids, such asspray nozzles, atomizers, or the like. Formulations of the presentinvention can be used in precision farming techniques, in whichapparatus is employed to vary the amount of exogenous chemical appliedto different parts of a field, depending on variables such as theparticular plant species present, soil composition, and the like. In oneembodiment of such techniques, a global positioning system operated withthe spraying apparatus can be used to apply the desired amount of theformulation to different parts of a field.

The formulation, at the time of application to plants, is preferablydilute enough to be readily sprayed using standard agricultural sprayequipment. Preferred application rates for the present invention varydepending upon a number of factors, including the type and concentrationof active ingredient and the plant species involved. Useful rates forapplying an aqueous formulation to a field of foliage can range fromabout 25 to about 1,000 liters per hectare (l/ha) by spray application.The preferred application rates for aqueous solutions are in the rangefrom about 50 to about 300 l/ha.

Many exogenous chemicals (including auxin herbicides) must be taken upby living tissues of the plant and translocated within the plant inorder to produce the desired biological (e.g., herbicidal) effect. Thus,it is important that an herbicidal formulation not be applied in such amanner as to excessively injure and interrupt the normal functioning ofthe local tissue of the plant so quickly that translocation is reduced.However, some limited degree of local injury can be insignificant, oreven beneficial, in its impact on the biological effectiveness ofcertain exogenous chemicals.

The experiments were carried out in greenhouse testing. The herbicidalformulations were applied postemergence to weeds having a height ofabout 10-15 cm using plot sprayers. Test formulations were applied at aspray volume 93 L/ha applied by means of a Flatfan 9501E nozzle(Spraying Systems Co., Wheaton, Ill., USA) at 165 kPa pressure. Thegreenhouse temperature was 21-29° C. at approximately 30% relativehumidity. Evaluation was done by visual scoring. The effects on theplant species were estimated in comparison with untreated control plotsusing a percentage scale (0-100%).

The components in Table 1 below are used in the Examples.

TABLE 1 Component Description Surf1 Tallowamine ethoxylate 10EOsurfactant Surf2 5:2:1:1 ratio of tallowamine ethoxylate (10.5EO)surfactant (Ethomeen T105 tallowamine ethoxylate):tridecanol phosphate(4EO) surfactant (Emphos PS-121 HM):polyethylene glycol(PEG400/600):dipropylene glycol Surf3 Surfonic AGM 550 surfactant Surf4Witconate AOK (sodium C₁₄₋₁₆ olefin sulfonate) Surf5 Tergitol 15-S-12surfactant Surf6 Ethylan 68-30 surfactant Surf7 Phosphalan PS-131 Surf8Agrimul 2067 APG surfactant Surf9 Ethomeen YT (12EO) (Tallow Y-amine12EO) Surf10 Ethoduomeen CD (3EO) (Alkoxylated N-coco-1,3-diaminopropane) Surf11 Adogen 570 (13EO) Surf12 Ethomeen YT (16EO)Surf13 Triamine Y/12 (Alkoxylated N- tallowalkyldipropylenetriamine)Surf14 Ethomeen Y/12 (8EO) (Alkoxylated N- tallowalkylamine) Surf15Ethomeen YT (8EO) Surf16 Adogen 560 (4.8EO) Surf17 Ethomeen YT (20EO)Surf18 Ethomeen Y/12 (12EO) Surf19 Adogen 560 (10EO) Surf20 Adogen 560(13.4EO) Surf21 Tetrameen T (4.9EO) Surf22 Corsamine TRT (19.2EO)(Alkoxylated N- tallowalkyldipropylenetriamine) Surf23 Ethomeen Y/12(16EO) Surf24 Heptamine YT (8EO) Surf25 Adogen 670 (14.9EO) Surf26Ethomeen Y/12 (4EO) Surf27 Ethomeen Y/12 (20EO) Surf28 Ethomeen YT (4EO)Surf29 Agnique PG 8107 Surf30 Tallowamine 15EO Surf31 Surfonic L12-8Surf32 Surfonic L24-9 Surf33 Surfonic L24-12 Surf34 Neodol 45-13 Surf35Tergitol 15-S-5 Surf36 Polyvinyl alcohol (77,000 to 79,000 molecularweight - CAS No. 9002-89-5) Surf37 Tomah E-17-5 Surf38 Witconate 93-SSurf39 Phospholan PS-236 Surf40 Surfonic L68-20 Surf41 Armeen APA 2Surf42 Armeen APA 6 Surf43 Armeen APA 8, 10 Surf44 Armeen APA 12 Surf45ACAR 7051 Surf46 ACAR 7059 Surf47 Adsee C80W Surf48 Tallowamineethoxylate (15EO) and glycerin Surf49 Ethomeen T/20H Poly1 Lupasol P(750,000 Dalton molecular weight) Poly2 Lupasol FG (800 Dalton molecularweight) Poly3 Aldrich Polyamine (molecular weight 25,000 Catalog No.408727) Poly4 Lupasol SC-61-B (110,000 Dalton molecular weight) Poly5Lupasol SK (2,000,000 Dalton molecular weight) Poly6Polyvinylpyrrolidone K30 (molecular weight 40,000, TCI cat no. P0472)Poly7 Quadrol Polyol Poly8 Lupasol HF (25,000 Dalton molecular weight)

Example 1

An experiment was performed to determine the efficacy of experimentalapplication mixtures prepared by aqueous dilution of experimental MEAdicamba salt formulations containing a surfactant relative tocomparative application mixtures prepared by dilution of the commercialproducts CLARITY and BANVEL.

Aqueous formulations comprising MEA dicamba were typically prepared bymixing water and monoethanolamine for 5 min followed by addition ofdicamba acid (98.3% purity) in one portion. The resulting suspensionswere stirred until all of the solids had dissolved by visual inspection,typically between 60 min and overnight. Relative amounts of dicamba andMEA used to give 61% by wt solutions of dicamba are reported in Table1a. These and MEA dicamba solutions prepared using this procedure weresubsequently used in preparation of MEA dicamba formulations containingpolyimine polymers and/or surfactants.

TABLE 1a Dicamba Water MEA Dicamba mol eq wt % (g) (g) (g) MEA:dicamba61 108.28 81.45 310.27 0.95 61 103.99 85.74 310.27 1.00 61 99.7 90.02310.27 1.05 61 57.27 56.58 186.15 1.10

The formulation of the experimental dicamba aqueous formulations areindicated in Table 1b below where the dicamba concentrations arereported on a weight percent active equivalent (wt % a.e.) basis unlessotherwise indicated. CLARITY contains 56.8 wt % active ingredient (a.i.)(38.5 wt % a.e.) of the diglycolamine salt of dicamba. BANVEL contains48.2 wt % a.i. of the dimethylamine salt of dicamba.

TABLE 1b Form. Dicamba concentration Component Comp. conc. 925S3J 48 wt% MEA dicamba Surf1 10 wt % 926Y7O 48 wt % MEA dicamba Surf2 10 wt %931F5L 40 wt % MEA dicamba Poly1 4.2 wt % 956N5T 48 wt % MEA dicambaSurf3 10 wt % 933C3S 40 wt % MEA dicamba Poly5 4.2 wt % 942T3R 55 wt %DGA Dicamba None — 944L8M 40 wt % DGA dicamba None — 957Y2S 61 wt % MEAdicamba None — 959C9L 48 wt % MEA dicamba Surf4 10 wt % 960U4V 40 wt %MEA dicamba Surf5 10 wt % 961X6A 48 wt % MEA dicamba Surf6 10 wt %962P0H 40 wt % MEA dicamba None — 963E2Z 48 wt % MEA dicamba Surf7 10 wt% 968Q3W 48.5 wt % MEA dicamba None — 416B5G 48 wt % MEA dicamba Surf814.3 wt % 955C3D 40 wt % MEA dicamba surf3 10 wt % 403E5Y 45 wt % MEAdicamba None — 416U7M 48 wt % MEA dicamba surf8 10 wt % 802R2X 48.1 wt %MEA dicamba surf7 10 wt % 929P6H 40 wt % MEA dicamba poly5 17.3 wt %908D1S 40 wt % MEA dicamba poly5 17.3 wt % surf2 8 wt % 066P9C 39.5 wt %MEA dicamba poly6 3 wt % 068I4B 39.5 wt % MEA dicamba poly6 10 wt %070J7X 48 wt % MEA dicamba poly6 8 wt % 071Q5H 48 wt % MEA dicamba poly64 wt % 532U3W 47.9 wt % MEA dicamba poly7 5 wt % 580Q7N 40 wt % DGAdicamba Poly2 4 wt % 7601W8J 40 wt % DGA dicamba Poly2 1 wt % 7602G5V 40wt % DGA dicamba Poly2 2 wt % 7603A1D 40 wt % DGA dicamba Poly2 3 wt %7604P0K 40 wt % DGA dicamba Poly2 4 wt % 7605L6Y 40 wt % DGA dicambaPoly2 5 wt % 7606M4R 40 wt % DGA dicamba Poly2 6 wt % 7191U4V 40 wt %potassium Poly2 1 wt % dicamba 7192E8K 40 wt % potassium Poly2 2 wt %dicamba 7193E3C 40 wt % potassium Poly2 3 wt % dicamba 7194R5X 40 wt %potassium Poly2 4 wt % dicamba 7195O7T 40 wt % potassium Poly2 5 wt %dicamba 7196M9K 40 wt % potassium Poly2 6 wt % dicamba 1381X4R 40 wt %potassium Poly8 1 wt % dicamba 1382P2H 40 wt % potassium Poly8 2 wt %dicamba 1383T5B 40 wt % potassium Poly8 3 wt % dicamba 1384U5U 40 wt %potassium Poly8 4 wt % dicamba 1385A4S 40 wt % potassium Poly8 5 wt %dicamba 1386J7G 40 wt % potassium Poly8 6 wt % dicamba 8145A6B 40 wt %DGA dicamba Surf2 12 wt % 8145B7U 40 wt % DGA dicamba Surf2 8 wt %8145C2Z 40 wt % DGA dicamba Surf2 4 wt % 8146A8A 40 wt % DGA dicambaSurf49 12 wt % 8146B2K 40 wt % DGA dicamba Surf49 8 wt % 8146C9K 40 wt %DGA dicamba Surf49 4 wt % 8147A1E 40 wt % DGA dicamba Surf48 12 wt %8147B8N 40 wt % DGA dicamba Surf48 8 wt % 8147C4F 40 wt % DGA dicambaSurf48 4 wt % Na-Dicamba 42 wt % Sodium — — Dicamba MEA-Dicamba 45 wt %MEA dicamba — — K-dicamba 53 wt % Potassium — — Dicamba

Formulations from Table 1 b and CLARITY were sprayed over the top ofsoybeans having both dicamba resistant and Roundup Ready® (RR) traits toinvestigate any possible injury at application rates of 561 (the labeledrate), 1120 and 2244 grams acid equivalent per hectare (kg a.e./ha) inthe equivalent of 93 liters per hectare (L/ha) water. Ratings were takenat 4 days after treatment (DAT). The data is presented in Table 1c in anANOVA summary of formulations mean comparisons by rate.

TABLE 1c 1120 g a.e./ha 2240 g a.e./ha 4480 g a.e./ha CLARITY 1.2 3.25.2 925S3J 1 4.5 11.3 926Y7O 0 4 12.7 956N5T 2.3 12.5 21.7 959C9L 0.83.2 20 960U4V 1.8 11.7 32.5 961X6A 1.2 6.5 20.8 962P0H 0.5 2.8 4.2963E2Z 0.5 7.3 31.7 416B5G 1.5 6.5 23.3 LSD 2.4 5 7.6

At the label use rate (1120 g a.e./ha), no significant injury was noted.The 4x label application rate of 4480 g a.e./ha indicated crop injury,particularly for formulation 960U4V containing an alcohol ethoxylatesurfactant. Overall, at normal use rates, none of the formulationsappear to be overly injurious to soybeans having dicamba resistant andRR traits.

The efficacy of application mixtures prepared from the Table 1 bformulations, CLARITY and BANVEL were evaluated on velvetleaf (ABUTH);common ragweed (AMBEL); pitted morningglory (IPOLA); and commonwaterhemp (AMATA). For each trial, dicamba was applied at rates of 140,280 and 561 grams a.e./ha in the equivalent of 93 L/ha of water. Ratingswere taken at 18 to 21 days after treatment DAT. The results of allrates were combined in a pair-wise T-test for each rating for theoverall ratings.

The result of the efficacy trials on ABUTH, AMBEL and IPOLA is reportedin Table 1d as t-test pairwise mean difference comparisons of CLARITYversus the experimental formulations and BANVEL and in Table 1e ast-test pairwise mean difference comparisons of BANVEL versus theexperimental formulations and CLARITY. A negative difference valueindicates that the experimental formulation provided increased efficacyrelative to the comparative formulations. For instance, in Table 1c,formulation 956N5T gave significantly higher combined weed control ascompared to CLARITY.

TABLE 1d CLARITY Combined Data ABUTH versus Difference n Difference n956N5T −11.9^(a) 126 −13.5^(a) 108 963E2Z −9.7^(a) 90 −12^(a)   72926Y7O −9.2^(a) 153 −12.2^(a) 108 960U4V −8.8^(a) 153 −12.4^(a) 108959C9L −8.7^(a) 153 −13.5^(a) 108 961X6A −7.3^(a) 153 −11.9^(a) 108925S3J −6.9^(a) 153  −9.5^(a) 108 Na-Dicamba −6.5^(a) 36  −6.5^(a) 36955C3D −6.3^(a) 135 −11.2^(a) 90 K-Dicamba −4.9^(a) 36  −4.9^(a) 36BANVEL −4.6^(a) 135  −7.5^(a) 90 416B5G −3.9^(a) 135  −8.8^(a) 90MEA-Dicamba −3.4^(a) 108 −4^(a)  90 CLARITY AMBEL IPOLA versusDifference n Difference n 956N5T — — −2.4^(c) 18 963E2Z — — −0.6^(c) 18926Y7O −3.0^(c)  27 −0.8^(c) 18 960U4V 0.3^(c) 27 −1.1^(c) 18 959C9L4.4^(c) 27 0.4^(c) 18 961X6A 5.9^(c) 27 0.7^(c) 18 925S3J −0.4^(c)  27−0.6^(c) 18 Na-Dicamba — — — — 955C3D 5.9^(c) 27 −0.2^(c) 18 K-Dicamba —— — — BANVEL 2.6^(c) 27 −1.0^(c) 18 416B5G 9.0^(d) 27 1.2^(c) 18MEA-Dicamba — — −0.4^(c) 18^(a) Formulation is significantly more efficacious than the standard(p<0.01)^(b) Formulation is significantly more efficacious than the standard(p<0.05)^(c) Formulation cannot be distinguished from the standard (p<0.05)^(d) Formulation is significantly less efficacious than the standard(p<0.05)^(e) Formulation is significantly less efficacious than the standard(p<0.01)

TABLE 1e BANVEL Combined Data ABUTH versus Difference n Difference n956N5T −4.8^(a) 108 −5.5^(a) 90 926Y7O −3.7^(a) 135 −4^(a)   90 959C9L−3.6^(a) 135 −6.2^(a) 90 960U4V −3.6^(a) 135 −4.6^(a) 90 963E2Z −3.3^(a)72 −4.5^(a) 54 961X6A −2.0^(c) 135 −4.4^(a) 90 925S3J −1.9^(b) 135−2.1^(a) 90 955C3D −1.7^(b) 135 −3.7^(a) 90 416B5G 0.7^(c) 135 −1.3^(c)90 Na-Dicamba 2.4^(d) 36  2.4^(d) 36 MEA-Dicamba 3.3^(e) 90 4^(e)  72K-Dicamba 3.9^(d) 36  3.9^(d) 36 CLARITY 4.6^(e) 135  7.5^(e) 90 CLARITYAMBEL IPOLA versus Difference n Difference n 956N5T — — −1.4^(c) 18926Y7O −5.5^(c)  27- 0.2^(c) 18 959C9L 1.9^(c) 27 1.4^(c) 18 960U4V−2.3^(c) 27 −0.1^(c) 18 963E2Z — — 0.4^(c) 18 961X6A 3.4^(c) 27 1.7^(c)18 925S3J −2.9^(c) 27 0.4^(c) 18 955C3D 3.3^(c) 27 0.8^(c) 18 416B5G6.5^(c) 27 2.2^(c) 18 Na-Dicamba — — — — MEA-Dicamba — — 0.6^(c) 18K-Dicamba — — — — CLARITY −2.6^(c) 27 1.0^(c) 18

The result of the efficacy trials, in % control at 17 DAT, on AMATA isreported in Table 1f.

TABLE 1f Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY59.2 68 72 962P0H 55 70.8 75 925S3J 57 76 94.2 926Y7O 62 79 91.3 956N5T65 78 94.7 959C9L 64 75 95 960U4V 63.3 72.5 93 961X6A 67.5 70 96.7963E2Z 67.5 87.5 99 929P6H 71.7 80.8 93.8 908D1S 63.3 72.5 100 LSD 8.711 7

At the highest application rate of 561 g a.e./ha all experimentalformulations gave superior efficacy as compared to MEA dicamba (962P0H)and CLARITY. At the application rate of 280 g a.e./ha, formulations963E2Z and 929P6H were more efficacious than CLARITY. At the lowestapplication rate of 140 g a.e./ha, formulation 929P6H was moreefficacious than CLARITY. In general, the formulations containingpolyimine polymers (Formulations 929P6H and 908D1S) provided equivalentherbicide performance as compared to formulations comprising asurfactant.

The result of the efficacy trials, in % control, on CHEAL is reported inTable 1g. The CHEAL was at the 9-12 leaf growth stage and was 10-15 cmin height.

TABLE 1g Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY27.5 50 68.3 962P0H 34.2 50 70.8 925S3J 75.8 89.2 96 926Y7O 79.2 89.793.2 956N5T 77.5 81.7 85.5 959C9L 58.3 80 89.3 960U4V 58.3 81.7 86.7961X6A 57.5 75.8 86.7 963E2Z 55.8 75 84.2 929P6H 53.3 61.7 87.5 908D1S59.2 77.5 86.7 LSD 7.8 6.5 5.5

At the 140 g a.e./ha application rate, all dicamba formulations weresuperior to the MEA dicamba salt formulation (962P0H) and CLARITY. Amongthe highest efficacy formulations at that rate were 925S3J, 926Y7O and956N5T. At the 280 g a.e./ha application rate, all dicamba formulationswere superior to the MEA dicamba salt formulation (962P0H) and CLARITY.The highest efficacy formulations at that rate were 925S3J and 926Y7O.At the 561 g a.e./ha application rate, all dicamba formulations exceptwere superior to the MEA dicamba salt formulation (962P0H) and CLARITY.The highest efficacy formulations at that rate were 925S3J and 926Y7O.

The result of the efficacy trials, in % control, on IPOLA is reported inTable 1 h. The IPOLA was at the 1-2 leaf growth stage and was 5-10 cm inheight.

TABLE 1h Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY83.3 98.8 99.5 403E5Y 83.8 99.5 99.7 BANVEL 85 99.8 99.8 925S3J 85.5 98100 926Y7O 89.7 94.8 99.5 955C3D 85 97.5 99.8 956N5T 89.2 100 99.7959C9L 82.5 98 100 960U4V 85 99.8 100 961X6A 81.7 98.2 99.7 416U7M 80.897.3 100 802R2X 83.3 100 100 LSD 9.6 3.2 0.5

At the 140 g a.e./ha application rate, 926Y7O was slightly lessefficacious than the other formulations.

The result of the efficacy trials, in % control at 15 DAT, on IPOLA isreported in Table 1i. The IPOLA was at the 1-2 leaf growth stage and was5-10 cm in height.

TABLE 1i Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY83.3 98.8 99.5 403E5Y 83.8 99.5 99.7 BANVEL 85 99.8 99.8 925S3J 85.5 98100 926Y7O 89.7 94.8 99.5 955C3D 85 97.5 99.8 956N5T 89.2 100 99.7959C9L 82.5 98 100 960U4V 85 99.8 100 961X6A 81.7 98.2 99.7 416U7M 80.897.3 100 802R2X 83.3 100 100 LSD 9.6 3.2 0.5

At the 140 g a.e./ha application rate, 926Y7O was slightly lessefficacious than the other formulations.

The result of the efficacy trials, in % control at 18 DAT, on ABUTH isreported in Table 1j. The ABUTH was at the 5-6 leaf growth stage and was10-15 cm in height.

TABLE 1j Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY25 52 79 962P0H 36 58 84 929P6H 39 59 85 926Y7O 44 67 90 066P9C 39 68 82068I4B 28 54 74 070J7X 38 58 84 071Q5H 41 65 83 532U3W 32 58 83 LSD 7.558 83

At the 140 g a.e./ha application rate, all six formulations of thepresent invention gave greater efficacy than CLARITY. At the applicationrate of 280 g a.e./ha, formulations 926Y7O, 066P9C and 071Q5H were moreefficacious than CLARITY. At the application rate of 561 g a.e./ha,formulation 926Y7O was more efficacious than CLARITY. The data appear toindicate that higher efficacy is achieved at lower polyvinylpyrrolidoneloading.

The result of the efficacy trials, in % control at 21 DAT, on ABUTH isreported in Table 1 k. The ABUTH was at the 5-6 leaf growth stage andwas 10-15 cm in height.

TABLE 1k Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY36.7 63.3 79.2 962P0H 36.7 64.2 82.5 925S3J 42.5 64.2 84.2 926Y7O 39.270 92.2 956N5T 45 72.5 88.3 959C9L 47.5 71.7 91.3 960U4V 45.8 78.3 92.2961X6A 45.8 65.8 91.8 963E2Z 41.7 75 88.3 929P6H 44.2 75.8 90.5 908D1S45 73.3 85 LSD 4.9 7.3 4.8

At the 140 g a.e./ha application rate, all formulations of the presentinvention except 926Y7O gave greater efficacy than CLARITY. At theapplication rate of 280 g a.e./ha, formulations 956N5T, 959C9L, 960U4V,963E2Z, 929P6H and 908D1S were more efficacious than CLARITY. At theapplication rate of 561 g a.e./ha, all formulations of the presentinvention were more efficacious than CLARITY and MEA dicamba (962P0H).

The result of the efficacy trials, in % control at 21 DAT, on Whiteclover (TRFRE) is reported in Table 1l. The TRFRE was at greater than 12leaf growth stage and was 10-15 cm in height.

TABLE 1l Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY45 62 76 962P0H 44 63 73 925S3J 51 74 80 926Y7O 53 62 85 956N5T 62 79 86959C9L 52 70 78 960U4V 60 78 84 961X6A 58 67 89 963E2Z 56 73 83 929P6H56 59 81 908D1S 55 66 83 LSD 6.5 7.5 7.1

At the 140 g a.e./ha application rate, all formulations of the presentinvention except 925S3J gave greater efficacy than CLARITY and MEAdicamba. At the application rate of 280 g a.e./ha, formulations 956N5T,959C9L, 960U4V, 963E2Z and 925S3J were slightly more efficacious thanCLARITY. At the application rate of 561 g a.e./ha, formulations 956N5T,926Y7O, 960U4V and 961X6A were slightly more efficacious than CLARITY.

Overall, the data of Tables 1b through 1k show that the herbicidalperformance of dicamba can be improved as compared to the commercialproducts CLARITY and BANVEL. The etheramine surfactant Surfonic AGM 550surfactant and surf2, comprising a mixture of a cationic alkyl etheramine surfactant and an anionic alkyl ether phosphate surfactant,provided the greatest dicamba herbicidal activity. Of the surfactants,the alkylpolyglucoside gave the least improvement also ABUTH control wasimproved as compared to CLARITY. The data further show that polymers cangive substantially equivalent dicamba efficacy enhancement as dosurfactants.

The efficacy of application mixtures prepared from Table 1bformulations, CLARITY, and 480 g/L MEA dicamba (formulations 943Q1H and944L8M) were evaluated on velvetleaf (ABUTH). For each trial, dicambawas applied post-emergent to 10-15 cm velvetleaf at rates of 140, 280and 560 grams a.e./ha. The results of the efficacy trial in % control at22 DAT are reported in Table 1m

TABLE 1m Formulation 140 g ae/ha 280 g ae/ha 560 g ae/ha 943Q1H 60.070.8 83.3 944L8M 65.8 78.3 85.0 7601W8J 70.0 79.2 91.7 7602G5V 61.7 69.280.0 7603A1D 60.0 68.3 74.2 7604P0K 58.3 68.3 79.2 7605L6Y 60.8 65.873.3 7606M4R 56.7 61.7 67.5 CLARITY 56.7 70.8 82.5 962P0H 63.3 66.7 74.2

The ANOVA summary of formulation mean comparisons by rate indicated thatat 140 g/L and 280 g/L 944L8M was more efficacious than CLARITY.Formulation 7601W8J was more efficacious than CLARITY at all 3 ratestested. At more than one rate, formulations 7605L6Y and 7606M4R wereless efficacious than CLARITY.

Potassium dicamba formulations from Table 1 b, CLARITY, and 480 g/L MEAdicamba were tested for their post-emergent control of 15 cm velvetleafat 70, 140, 280 and 560 grams a.e./ha. The results of the efficacy trialin % control at 22 DAT are reported in Table 1n.

TABLE 1n Form. 70 g ae/ha 140 g ae/ha 280 g ae/ha 560 g ae/ha 7191U4V31.7 55.0 65.8 79.2 7192E8K 40.0 55.8 65.8 78.3 7193E3C 45.0 56.7 65.873.3 7194R5X 32.5 51.7 62.5 75.0 7195O7T 42.5 64.2 70.0 84.2 7196M9K38.3 49.2 74.2 87.5 CLARITY 29.2 55.8 65.0 75.8 962P0H 37.5 55.0 67.576.7

All experimental formulations of potassium dicamba with polyiminepolymers from Table 1 n provided equivalent or superior control of ABUTHcompared to CLARITY.

Potassium dicamba formulations from Table 1 b, CLARITY, 962P0H, and931F5L were tested for their post-emergent control of 15 cm velvetleafat 70, 140, 280 and 560 grams a.e./ha. The results of the efficacy trialin % control at 22 DAT are reported in Table 1o

TABLE 1o Form. 70 g ae/ha 140 g ae/ha 280 g ae/ha 560 g ae/ha 1381X4R55.8 62.5 68.3 84.2 1382P2H 52.5 62.5 65.8 80.8 1383T5B 48.3 59.2 67.578.3 1384U5U 50.0 62.5 67.5 80.8 1385A4S 55.8 61.7 68.3 81.7 1386J7G54.2 65.0 66.7 81.7 CLARITY 50.8 63.3 72.5 85.8 931F5L 55.8 62.5 69.283.3 962P0H 50.0 65.0 70.8 85.0

The efficacy of certain application mixtures from Table 1b, CLARITY,962PoH and 931F5L were evaluated on velvetleaf (ABUTH). For each trial,dicamba was applied post-emergent to 15 cm velvetleaf at rates of 140,280 and 560 grams a.e./ha. The results of the efficacy trial in %control at 22 DAT are reported in Table 1p.

TABLE 1p Form. 140 g ae/ha 280 g ae/ha 560 g ae/ha 8145A6B 60.0 76.791.7 8145B7U 56.7 79.2 90.0 8145C2Z 51.7 75.0 90.0 8146A8A 64.2 79.292.5 8146B2K 58.3 81.7 92.5 8146C9K 64.2 73.3 90.8 8147A1E 58.3 82.592.5 8147B8N 58.3 79.2 92.5 8147C4F 55.8 80.0 91.7 Clarity 50.8 66.790.0 931F5L 61.7 75.8 90.8 962P0H 55.0 75.8 93.3

At 140 and 280 grams a.e./ha all experimental formulations from Table 1bprovided equivalent or superior control of ABUTH in comparison toCLARITY. At 540 grams a.e./ha all experimental formulations from Table1p were equivalent to CLARITY.

Example 2

Aqueous formulations comprising MEA dicamba and various coco and tallowdi- and tri-amine ethoxylates were prepared as indicated in Table 2awherein the dicamba concentration in each formulation was 633 g a.e./ha(47.9 wt % a.e.) and the concentration of the other components in wt %is indicated in parenthesis.

TABLE 2a Formulation 504A3F 504B5T 504C8N 504D3J MEA Dicamba 61 61 61 61Surfactant (wt %) Surf9 (10) Surf10 (10) Surf11 (10) Surf12(10)Formulation 504E7C 504F2I 504G0L 504H6T MEA Dicamba 61 61 61 61Surfactant (wt %) Surf13 (10) Surf14 (10) Surf15 (10) Surf16(10)Formulation 504I8L 504J4P 504K1B 504L9O MEA Dicamba 61 61 61 61Surfactant (wt %) Surf17 (10) Surf18 (10) Surf19 (10) Surf20(10)Formulation 504M6K 504N5U 504O7X 50P1F MEA Dicamba 61 61 61 61Surfactant (wt %) Surf21 (10) Surf22 (10) Surf23 (10) Surf24(10)Formulation 504Q3D 504R6E 504S9M 504T7Q MEA Dicamba 61 61 61 61Surfactant (wt %) Surf25 (10) Surf26 (10) Surf27 (10) Surf28(10)

The formulations from Table 2a and CLARITY were sprayed over the top ofvelvetleaf (ABUTH) plants evaluate herbicidal efficacy at applicationrates of 140, 280 and 561 g a.e./ha in the equivalent of 93 liters perhectare (L/ha) water. Herbicidal efficacy was evaluated at 22 days aftertreatment (DAT). The data is presented in Table 2b in an ANOVA summaryof formulations mean comparisons by rate.

TABLE 2b Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY42.5 59.2 79.2 926Y7O 45 58.3 79.2 504A3F 45 64.2 80 504B5T 42.5 63.382.5 504C8N 45 64.2 83.3 504D3J 49.2 65 83.3 504E7C 48.3 63.3 77.5504F2I 44.2 61.7 78.3 504G0L 49.2 66.7 80.8 504H6T 49.2 63.3 78.3 504I8L49.2 65.8 79.2 504J4P 50 68.3 81.7 LSD 4.1 4.5 4.9 CLARITY 46.7 69.2 85926Y7O 55 71.7 89.7 504K1B 52.5 77.5 89.2 504L9O 53.3 76.7 90.5 504M6K49.2 73.3 90.8 504N5U 51.7 80 90.5 504O7X 60 72.5 88.3 50P1F 52.5 71.790.5 504Q3D 55 76.7 88.3 504R6E 54.2 71.7 91 504S9M 46.7 72.5 87.5504T7Q 53.3 71.7 87.2 LSD 5.7 3.8 4.7

The experimental formulations were generally more efficacious than theCLARITY standard. None of the surfactants provided a clear efficacyadvantage on ABUTH at higher application rates. At lower applicationrates, the Ethomeen YT series of surfactants provided good ABUTHefficacy.

Example 3

The specific gravity and pH of potassium and MEA dicamba aqueoussolutions were evaluated. The results are reported in Table 3a wherein“Dicamba wt %” refers to weight percent acid equivalent dicamba insolution and “SG” refers to specific gravity in grams per mL. The pH ofMEA dicamba was measured for two lots of material.

TABLE 3a K Dicamba MEA Dicamba Dicamba wt % SG pH SG pH pH g a.e./L 51.03 5.4 1.02 6.6 8.3 — 10 1.05 5.4 1.05 6.7 8.4 — 15 1.09 5.4 1.07 6.88.5 — 20 1.12 5.9 1.09 6.9 8.55 — 25 1.15 6.3 1.12 7 8.6 — 30 1.18 6.51.14 7.1 8.65 291 35 1.22 6.8 1.17 7.3 8.7 391 40 1.25 7 1.2 7.4 8.8 47845 1.29 7.3 1.23 7.5 8.85 554 50 1.33 7.6 1.25 7.6 8.9 623 55 1.36 7.81.28 7.7 8.95 684 60 1.4 8.1 1.31 7.8 9 741

The data indicate that solutions of potassium dicamba have a greaterspecific gravity and lower pH at a given concentration than do solutionsof MEA dicamba.

In a set of experiments, the crystallization behavior of formulationscontaining MEA dicamba, potassium glyphosate and a surfactant wasevaluated. The formulation of the experimental dicamba formulations areindicated in Table 3b below where dicamba concentration is reported inwt % a.e., the surfactant concentration is reported in wt %, “SG” refersto specific gravity (20/18.6), “Ratio K:MEA” refers to the ratio (a.e.basis) of potassium glyphosate to MEA dicamba, “surf” refers tosurfactant, and “Xtals” refers to crystals. Approximately 3-5 mL of eachsolution was placed into a 60 mL jar and left uncovered in a fume hoodto dry at ambient humidity and temperature. The solutions were visuallyobserved periodically for the presence of crystalline residue as thewater evaporated from the solution.

TABLE 3b Form. 957A 857A 858A 858B 859A Ratio K:MEA 0:1 1:1 3:1 1:3 1:0K-gly wt % a.e. 0 23.6 36.1 12.1 46.3 MEA-dicamba wt % a.e. 61  23.612.1 36.1 0 surf. none surf3 surf3 surf3 surf3 wt % surf 0 10 10 10 10SG 1.2606 1.2859 1.249 1.2913 Xtals @1 day no yes yes no yes Xtals @3days no yes yes no yes Xtals @20 days no yes yes no yes Form. 864 865866 867 Ratio K:MEA 3:1 1:3 1:1 1:0 K-gly wt % a.e. 35 12.1 23.9 46.5MEA-dicamba wt % a.e. 11.6 36.1 23.9 0 surf. surf2 surf2 surf2 surf2 wt% surf 9.3 9.3 9.3 9.3 SG 1.2839 1.2589 1.276 1.3049 Xtals @1 day yes nono yes Xtals @3 days yes no yes yes Xtals @20 days yes no yes yes

In a second set of experiments, the crystallization behavior offormulations containing MEA dicamba, potassium glyphosate, a surfactantand 5 wt % glycerine was evaluated. The formulation of the experimentaldicamba formulations is indicated in Table 3c. The method describedabove for the date in Table 3b was used for crystallization evaluation.

TABLE 3c Form 877 878 879 Ratio K:MEA 1:0 1:0 1:0 K-gly wt % a.e. 46.446.4 46.4 MEA-dicamba wt % a.e. 0 0 0 surf. surf2 surf1 surf3 wt % surf10 10 10 wt % glycerin 5 5 5 SG 1.3189 1.3227 1.3082 Xtals @3 days yesyes yes

Example 4

The volatility of the sodium, potassium, DMA, MEA, IPA and DGA salts ofdicamba contained in aqueous formulations were measured in distillationexperiments.

Solutions of each of the sodium, potassium, DMA, MEA, IPA and DGA saltsof dicamba were prepared as 10% stock solutions at a mole ratio ofapproximately 1:1 dicamba acid to base. To alter the pH, either dicambaacid was added or base was added. The pH was measured on a standardOrion Model 320 pH meter of each neat solution. For the distillations,the salt solutions were diluted to obtain a dicamba concentration of 5%,2%, and 1% a.e. while compensating for any added base or dicamba acid toadjust pH. The Diglycolamine salt solutions were prepared usingClarity®, a 38.5% a.e. dicamba solution.

Simple distillation using a short path still was used to collect thewater distillate containing the dicamba in the vapor phase of the saltsolutions. A 50 mL distillation flask was used. The distillationreceiver was a “cow” type with four 2 mL graduated sections. Thesolutions were heated at the 30% setting of the GlassCol heating unitand the boiling point of each distillation was noted. The first 2 ml ofdistillate was collected, and the receiver rotated to avoid collectionof any further distillate in that section as the distillation flaskcooled. The 2 mL sample was quantitatively transferred by pipette toHPLC vials for later analysis. Between each distillation thedistillation apparatus was washed with 10 volumes of tap water, 10volumes of distilled water, rinsed with acetone, and dried in a 60° C.oven. Each distillation was run in triplicate.

The distillate was collected and analyzed for dicamba concentrationusing HPLC/Mass Spectroscopy (MS). The HPLC column was an Agilent ZorbaxEclipse XDB-C8, 4.6×150 mm, 5u, PN 993967-90. Mobile phase A was 0.1%formic acid in D.I. water. Mobile phase B was 0.1% formic acid inacetonitrile. A flow rate of 1.2 mL/min was used and an injection volumeof 5, 10, 15 or 25 ul was used depending on the dicamba level in thesample. The following gradient was used:

Time % A % B 0 100 0 7.5 0 100 10 0 100 10.1 100 0 15 100 0

The MS parameters were as follows: Type SIR; ES-ion mode; 0.05 secondinter channel delay; 0.05 second interscan time; 0.5 span (Da); 10minutes elapsed time; and 6-6000 ppb calibration range. Channel 1 masswas 175 (Da); Dwell was 0.25(s); Cone(V)=tune and; 0.05(s) delay.Channel 2 mass was 177 (Da); Dwell was 0.25(s); Cone(V)=tune and;0.05(s) delay.

Differences in the amount of dicamba in the distillate of dicamba saltsolutions were found with changing cation, concentration, and pH. Tables4a through 4f summarize the data for all experiments. These tables showthe mean values of Dicamba concentration in the distillate from thetriplicate distillations. The standard deviation is shown.

TABLE 4a Distillation and liquid chromatography/mass spectroscopy(LC/MS)results for Na Dicamba salt solution at varying pH andconcentration. % a.e. Solution Mean Dicamba in Standard Salt Dicamba pHDistillate (ppm) Dev Na 5% 3.36 11.57 0.498 Na 5% 4.34 2.36 0.047 Na 5%6.32 0.77 0.186 Na 5% 10.36 0.45 0.044 Na 5% 12.15 0.22 0.071 Na 2% 3.335.74 0.337 Na 2% 4.29 1.39 0.486 Na 2% 6.28 0.32 0.165 Na 2% 9.93 0.160.074 Na 2% 11.50 0.15 0.077 Na 1% 3.31 3.42 1.174 Na 1% 4.25 0.70 0.117Na 1% 6.19 0.13 0.013 Na 1% 9.82 0.09 0.022 Na 1% 11.15 0.06 0.020

TABLE 4b Distillation and LC/MS results for MEA Dicamba salt solution atvarying pH and concentration. % a.e. Solution Mean Dicamba in StandardSalt Dicamba pH Distillate (ppm) Dev MEA 5% 3.61 4.58 0.165 MEA 5% 4.441.71 0.518 MEA 5% 6.87 0.54 0.068 MEA 5% 8.03 0.27 0.054 MEA 5% 9.320.33 0.151 MEA 2% 2.90 12.05 NA MEA 2% 4.81 0.48 NA MEA 2% 4.89 0.36 NAMEA 2% 6.4 0.4 NA MEA 2% 7.25 0.25 NA MEA 2% 8.03 0.18 NA MEA 2% 9.210.1 NA MEA 1% 3.68 1.39 0.208 MEA 1% 4.34 0.39 0.075 MEA 1% 6.81 0.370.218 MEA 1% 7.84 0.08 0.019

TABLE 4c Distillation and LC/MS results for DGA Dicamba salt solution atvarying pH and concentration % a.e. Solution Mean Dicamba in StandardSalt Dicamba pH Distillate (ppm) Dev DGA 5% 4.57 2.11 1.154 DGA 5% 6.350.75 0.174 DGA 5% 8.26 0.58 0.082 DGA 5% 9.03 0.32 0.094 DGA 2% 4.171.10 0.275 DGA 2% 6.44 0.31 0.081 DGA 2% 8.22 0.28 0.129 DGA 2% 8.920.19 0.028 DGA 1% 4.23 0.46 0.032 DGA 1% 6.48 0.18 0.009 DGA 1% 8.240.13 0.030 DGA 1% 8.88 0.12 0.013

TABLE 4d Distillation and LC/MS results for IPA Dicamba salt solution atvarying pH and concentration % a.e. Solution Mean Dicamba in StandardSalt Dicamba pH Distillate (ppm) Dev IPA 5% 3.44 5.85 0.785 IPA 5% 4.333.14 0.482 IPA 5% 4.94 3.77 1.081 IPA 5% 8.24 2.47 0.170 IPA 5% 9.2812.57 1.502 IPA 2% 3.37 3.65 1.132 IPA 2% 4.36 1.42 0.625 IPA 2% 5.100.94 0.344 IPA 2% 8.13 0.75 0.118 IPA 2% 9.20 3.43 1.034 IPA 1% 3.411.42 0.283 IPA 1% 4.40 0.42 0.036 IPA 1% 5.13 0.37 0.082 IPA 1% 8.100.72 0.575 IPA 1% 9.13 1.22 0.088

TABLE 4e Distillation and LC/MS results for DMA Dicamba salt solution atvarying pH and concentration % a.e. Solution Mean Dicamba in StandardSalt Dicamba pH Distillate (ppm) Dev DMA 5% 3.18 20.10 3.212 DMA 5% 4.222.67 0.550 DMA 5% 5.58 2.06 1.184 DMA 5% 8.69 8.43 1.001 DMA 5% 10.1712.34 2.335 DMA 2% 3.20 9.19 1.315 DMA 2% 4.25 1.08 0.087 DMA 2% 5.970.83 0.161 DMA 2% 8.66 1.98 0.104 DMA 2% 10.24 4.88 3.060 DMA 1% 3.254.50 0.566 DMA 1% 4.36 0.57 0.052 DMA 1% 6.11 0.30 0.103 DMA 1% 8.530.73 0.079 DMA 1% 10.12 1.32 0.543

TABLE 4f Distillation and LC/MS results for Dicamba acid solution withvarying concentration wt % a.e. dicamba pH Dist ppm Std Dev 0.5 1.8419.6 5.3 1 <1.2 56.5 21.4 2 <1.2 151.1 11.2

For all of the solutions studied, as the concentration of Dicamba in thesolution increased, the amount of Dicamba in the distillate increased.The data suggests that pH significantly affects the amount of Dicambaentering the vapor phase. In distillations with salts of Na, K, MEA, andDGA, as the pH is increased, the amount of Dicamba measured in thedistillate is decreased. With the IPA and DMA salts, this trend holdsuntil the pH is 6-7, but at a higher pH values, the amount of Dicambameasured in the distillate is increased. The data show that the lowvolatility cation salts, Na, K, MEA and DGA, all have similarvolatilities at a given pH. In one explanation, the more volatilecations IPA and DMA show more dicamba in the distillate at higher pHbecause as the solution distills, a significant amount of the cation(DMA or IPA) is distilling from the solution. This leads to aneffectively lower pH in the solution being distilled and a resultanthigher amount of dicamba being distilled from the solution. Anotherpossible explanation is that the volatile cations are co-distilling fromthe solutions with dicamba, particularly when the original pH of thedistillation solution is greater than 7.

To investigate the increased volatility with the DMA salt at a pHgreater than about 6 to 7, the concentration of the amine was measuredin the distillate in a separate experiment, and is shown in Table 4g.The data shows that at higher pH there is a larger amount of amineentering the vapor phase. It is also significant to note that at anacidic pH (3.6) there was no detectable amine in the distillate by HPLCanalysis. The data also show a resulting lowering of the pH from thesolution in the distillation flask from loss of amine as one mightexpect from distillation of the base from the solution.

TABLE 4g pH and concentration of dimethylamine after distillation of 5%a.e. DMA Dicamba solutions Starting pH Solution ppm DMA Solution pHAfter Distillation in Distillate 3.60 3.58 Undetectable 8.20 7.04  400ppm 10.10 6.4 5000 ppm

Table 4h provides a summary of dicamba in the distillate of 5% a.e.Dicamba solutions at approximately neutral pH. While it is difficult todirectly compare the values as the pH of each solution is slightlydifferent, the relative difference are clear that the more volatileamine salts have a higher concentration of dicamba in the distillatecompared to the lower volatile cation salts DGA Na, K, and MEA. Theselower volatility salts also showed a pH dependent trend of lower amountsof dicamba in the distillate as the pH increases.

TABLE 4h Dicamba concentration in distillate for 5% a.e. salt solutionsat the near neutral pH Salt pH ppm Dicamba in distillate Na 6.32 0.8 K7.06 0.6 MEA 6.87 0.5 MEA 8.03 0.3 DGA 6.35 0.8 DGA 8.26 0.6 DMA 5.582.1 DMA 8.69 8.4 IPA 8.24 2.5

In a further set of experiments, measurements of dicamba concentrationin the gas phase (air) above 38.5 wt % a.e. solutions of various dicambasalts was measured. 5 mL of each sample of dicamba was placed into a 50mL plastic centrifuge tube with four holes approximately ⅛ in diameterdrilled into the tube at the 10 mL line. A 22 mm×30 mm PUF (SKC ct.#226-124) was placed into a glass tube of app. 20 mm diameter withparafilm wrapped around the outside to obtain a snug fit into the top ofthe centrifuge tube. A hose was connected to the other end of the glasstube leading to a vacuum line. The air flow was regulated to app. 2L/min using a flow controller (about 0.4 L air/min-mL sample). Air waspulled through the tube at app. 1 L/min for approximately 1 day. Notethat the air conditions of flow rate, temperature, pressure andcomposition (e.g., relative humidity) are not narrowly critical as longas the various samples are analyzed under similar conditions. Forinstance, air at from about 5° C. to about 40° C., from about 0.5 toabout 1.5 bar pressure, from about 0% to about 95% relative humidity,and at a flow rate of from about 0.1 to 10 L/min-mL sample could besuitably used for volatility analysis. The PUF was removed from theglass tube, extracted with 20 mL methanol and the resulting solutionanalyzed for dicamba concentration by LC-MS. The results are shown inTable 4i below where “wt % a.e.” refers to the dicamba concentration,“μg/m L” refers to the dicamba concentration in the distillate, “μgdicamba” refers to the total dicamba extracted from the PUF by 20 mLmethanol, and “ng/L air” and “moles/L air” refer to the dicambaconcentration in the gas phase above the solution.

TABLE 4i wt % μg/ μg ng/L moles/L Dicamba salt a.e. mL dicamba air airsodium (pH 2.7) 35.8 3.55 71 9.86 4.46 × 10⁻¹¹ potassium (pH 10.5) 35.80.24 4.8 0.67 3.02 × 10⁻¹² MEA 35.8 0.02 0.4 0.056 2.51 × 10⁻¹³ BANVEL(DMA salt) 40 0.42 8.4 1.17 5.28 × 10⁻¹² dicamba acid 99 15.3 305.4 42.41.92 × 10⁻¹⁰

The MEA salt showed a dicamba concentration in the gas phase above thesolution lower than the acid or the sodium, potassium and DMA salts.Notably, the MEA salt had a gas concentration on the order of 20 timesless than the commercial product BANVEL.

In a further set of experiments, measurements of dicamba concentrationin the gas phase (air) above 10 wt % a.e. solutions of various MEAdicamba formulations and CLARITY (DGA dicamba salt) was measured. Themethod was as follows:

Equipment: Polyurethane Foam (PUF) plug approximately 22 mm×30 mmavailable from SKC Inc., cat. No. CPM100108-003; 50 mL PET, Centrifugetube, Corning cat No. 430290, with a hole drilled into the wall app. ½inch above the 20 mL line on the tube with a ⅛ inch drill bit; Glasstube to hole the PUF app. 30 mm iD with a nipple on one end to attach toa Tygon Tube; Ring Stand; Parafilm; Air Pump; ConstantHumidity/temperature chamber, such as a growth chamber or Incubator;Solutions of dicamba.

Procedure: The procedure took place in a growth chamber at a temperatureof 35° C. and relative humidity of 30%. A PUF was placed into the glasstube. The top of the tube was wrapped with parafilm such that it wouldfit snuggly into the top of the centrifuge tube. 10 mL of the dicambaa.e. solution prepared to be approximately 20% a.e. dicamba was placedinto the centrifuge tube. The tube was attached to the ring stand andheld in a vertical position. The glass tube was fitted into the top ofthe centrifuge tube. A tygon tube was connected to the nipple on theglass tube. This tube was connected to an air pump through a needlevalve to control the air flow at 2 liters per minute (about 0.2 Lair/min-mL sample). The air pump was started and air pulled through thetube for 24 hours. After 24 hours, the pump was turned off and the PUFremoved from the glass tube. The PUF was placed into 20 mL of methanolto extract the dicamba. The amount of dicamba was quantified by LC/MassSpectrometric analysis.

The results are shown in Table 4j below wherein formulations 506C3N,5851AR and 566E7H each contained Lupasol SK polymer (poly5) at a 1:1weight ratio of dicamba a.e. to polymer and formulations 5851BT and565B8I each contained dicamba MEA in the absence of polymer. Thereported results for formulation 506C3N is the average of 6 samples,each tested in duplicate, and the remaining results represent theaverage of 4 samples, each tested in duplicate. In the table, “S.D.”refers to standard deviation, “% RSD” refers to percent relativestandard deviation and “Form. pH” refers to the pH of the dicambaformulation.

TABLE 4j Dicamba Dicamba Form. (ng/L) (ng/L) S.D. % RSD Form. pH 506C3N0.111 0.049 44.05 8.26 CLARITY 0.696 0.066 9.50 6.94 5851AR 0.036 0.01027.42 9.43 5851BT 0.047 0.017 35.77 9.62 CLARITY 0.611 0.072 11.78 6.94566E7H 0.138 0.088 63.61 6.92 565B8I 1.513 0.172 11.34 7.16

The data indicate that Lupasol reduced MEA dicamba volatilization byabout 25% at a pH of about 9.5 and by about 1000% at a pH of about 7.

In a further set of experiments, measurements of dicamba concentrationin the gas phase (air) above 10 wt % a.e. solutions of various MEAdicamba formulations, CLARITY (DGA dicamba salt) and BANVEL (DMA dicambasalt) were measured and are reported in Table 4k below. The method wasas described above for the data of Table 4j. The reported results arethe average of 4 or 6 samples, each tested in duplicate. In the table,“Form.” refers to formulation number, “ng/L” refers to the dicambaconcentration above the 10 wt % a.e. dicamba solutions, “SD” refers tostandard deviation, “pH” refers to the pH of the formulation, “Test mL”refers to the volume of dicamba solution tested and “Ratio” refers tothe weight ratio of dicamba a.e. to polymer where the identity of thepolymer is indicated in parentheses.

TABLE 4k Form. ng/L SD pH Test mL Ratio (polymer) CLARITY 0.65 0.08 6.910 no polymer CLARITY 1.17 0.06 6.98 20 no polymer CLARITY 0.41 0.02 7.810 no polymer CLARITY 0.05 0.02 7.8 10 8:1 (poly5) BANVEL 3.43 1.59 6.1410 no polymer BANVEL 5.68 2.21 6.38 20 no polymer BANVEL 1.53 0.32 8.110 no polymer 565K8T 16.53 0.94 3.2 10 no polymer 565L9U 1.78 0.20 6.0610 no polymer 565M7G 0.88 0.12 6.12 10 no polymer 565N3K 1.22 0.10 7.0810 no polymer 565B8X 1.51 0.17 7.16 10 no polymer 565B8X 3.56 0.59 7.1720 no polymer 565O2V 0.48 0.05 8.01 10 no polymer 957Y2S 0.98 0.31 8.4420 no polymer 565C6L 0.38 0.13 8.53 20 no polymer 565D0J 0.19 0.04 9.0420 no polymer 5851BR 0.05 0.02 9.62 10 no polymer 565CC8I7 0.21 0.047.09 10 8:1 (poly1) 565DD2K9 0.17 0.03 8.05 10 8:1 (poly1) 565EE3E2 0.050.01 9.12 10 8:1 (poly1) 565P5G 0.17 0.01 5.73 10 8:1 (poly5) 566E6Y0.14 0.09 6.92 10 8:1 (poly5) 506C7J 0.25 0.08 8.23 20 8:1 (poly5)506C7J 0.54 0.18 8.24 20 8:1 (poly5) 506D9P 0.18 0.05 8.74 20 8:1(poly5) 5851AT 0.04 0.01 9.43 10 8:1 (poly5) 565Q9L 1.10 0.24 7.19 10100:1 (poly5) 565R7F 0.31 0.09 8.03 10 100:1 (poly5) 565S3T 0.06 0.018.98 10 100:1 (poly5) 565T4V 0.44 0.03 7.62 10 20:1 (poly5) 565U8S 0.200.10 8.24 10 20:1 (poly5) 565V7M 0.05 0.02 9.25 10 20:1 (poly5) 565W0J0.50 0.15 7.19 10 100:1 (poly2) 565Y1U 0.25 0.06 9.03 10 100:1 (poly2)565X3Y 0.06 0.03 9.00 10 100:1 (poly2) 565Z5R 0.34 0.28 7.37 10 20:1(poly2) 565AA3B 0.14 0.04 8.26 10 20:1 (poly2) 565BB7H 0.04 0.02 9.17 1020:1 (poly2)

The results indicate that polymer reduces dicamba volatility. At pH 7,even a 100:1 weight ratio of dicamba a.e. to polymer provided a smallvolatility reduction.

Example 5

Aqueous formulations comprising 601 g a.e./L MEA dicamba (48.3 wt %a.e.) were combined with from 1 to 10 wt % polyimine polymers having arange of molecular weights as indicated in Table 5a below. Each of theformulations was a clear solution.

TABLE 5a Component 1 Component 2 Formulation Polymer wt % Surfactant wt% 151J6M — — — — 152F5X — — Surf3 6 153P0L Poly1 5 — — 154V4V Poly1 5Surf3 6 161L8I Poly2 5 — — 162N4R Poly2 5 Surf3 6 163L1K Poly3 5.7 — —164A2D Poly3 5 Surf3 6 171H3P Poly4 7.6 — — 172G5F Poly4 7.6 Surf3 6

The formulations from Table 5a, previously described formulations962P0H, 926Y7O, 956N5T, formulation 962-2A (containing 480 g a.e./L (40wt % a.e.) MEA dicamba with no surfactant, and CLARITY were appliedpostemergence at rates of 140, 280 and 561 g a.e./ha on 10-15 cm highVelvetleaf and evaluated 18 days after treatment. The results in %control are reported in Table 5b below.

TABLE 5b Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY58.3 86.7 91.8 962P0H 52.5 86.7 91.7 962-2A 70.8 87.5 93 926Y7O 65.8 8595.7 956N5T 65.8 86.7 94.3 151J6M 70.8 87.5 93 152F5X 62.5 86.7 95.2153P0L 70.8 87.5 93 154V4V 68.3 88.3 91.7 161L8I 72.5 85 92.2 162N4R58.3 85 97.5 163L1K 73.3 90 91.7 164A2D 67.5 88.3 93 171H3P 66.7 85.893.5 172G5F 69.2 85.8 93 LSD 6.5 5.6 3.9

The bioefficacy data shows an increase in dicamba activity at anapplication rate of 140 g a.e./ha and no reduction in dicamba activityat application rates of 280 and 561 g a.e./ha for the formulationscomprising the polymers as compared to formulations comprising asurfactant in the absence of a polymer or the combination of asurfactant and a polymer. At an application rate of 140 g a.e./ha,formulations 151 J6M, 153P0L, 154V4V, 161 L8I, 163L1K and 172G5F weresignificantly more efficacious than CLARITY.

Example 6

Aqueous formulations comprising 600 g a.e./L MEA dicamba (48.3 wt %a.e.) were prepared as indicated in Table 6a below where “Form” refersto formulation. All of the formulations were clear, homogeneoussolutions. The formulations were evaluated for spraying characteristics.

TABLE 6a Component 1 Component 2 Form polymer wt % Surfactant wt %019A8J Poly5 3.5 — — 019B6Y Poly5 3.5 Surf3 6 019C9J Poly5 6 — —

The formulations from Table 6a, previously described formulations151J6M, 152F5X, 962P0H, 926Y7O and 956N5T and CLARITY were appliedpostemergence at rates of 140, 280 and 561 g a.e./ha on 10-15 cm highVelvetleaf and evaluated 18 days after treatment. The results in %control are reported in Table 6b below.

TABLE 6b Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY60.0 83.3 96.5 962P0H 68.3 84.2 98.5 926Y7O 71.7 87.5 97.7 956N5T 70.092.5 96.3 019A8J 71.7 88.3 96.3 019B6Y 72.5 91.7 98.3 019C9J 75.8 89.296.7 151J6M 75.0 87.5 95.5 152F5X 80.8 90.8 98.0 LSD 6.5 2.4 2.2

The formulations and the comparative formulation CLARITY were diluted inwater to a dicamba concentration of 0.77 wt % a.e. The dilutedformulations were sprayed using the method for greenhouse efficacytesting on plant, as describe above, on water sensitive paper thatchanges color (to blue) where a spray drop contacts the paper. TheCLARITY composition produced more color on the paper as compared toexperimental formulations 019A8J, 019B6Y and 019C9J. The experimentalformulations show a comparably more consistent drop size, but stillprovide good coverage over the paper. The results suggest thatpolyimines may result in fewer fine droplet particles as compared toCLARITY and can therefore provide some drift control properties to theformulations.

Example 7

The cold temperature stability of aqueous formulations comprising 480 ga.e./L MEA dicamba and 5 wt % polymer formulated at varied mole ratiosof MEA to dicamba was evaluated. For each test, approximately 50 mL ofeach formulation was placed into a glass bottle. The bottle were placedin an oven or freezer and evaluated after 1 and 4 weeks of storage andobserved for any layering, crystal formation or freezing. The pH wasevaluated by measurement after dilution to 1 wt % a.e. dicamba. Theformulation of the formulations and test results are reported in Table7a below wherein “MEA:dicamba” refers to the molar ratio of MEA base todicamba acid, “stable” refers to no phase separation, “Clr. Sln.” refersto clear solution, and “layer” refers to phase separation.

TABLE 7a MEA:mol 0.8:1 0.9:1 1:1 1.1:1 pH 3.87 4.77 8.19 8.94  60° C.Clr. Sln. Stable, Clr. Sln. Clr. Sln. Clr. Sln.  50° C. Stable StableClr. Sln. Clr. Sln.  0° C. Clr. Sln. Clr. Sln. Clr. Sln. Layer −10° C.Clr. Sln. Clr. Sln. Clr. Sln. Layer −20° C. Frozen Clr. Sln. Clr. Sln.Layer −30° C. Frozen Frozen Frozen Frozen

The results indicate that at high pH (8.9) layering occurs while atslightly lower pH (8.2) the formulation is stable.

Example 8

Aqueous formulations comprising 480 and 600 g a.e./L MEA dicamba wereformulated with varying amounts of Lupasol SK polymer (poly5). Viscositywas measured at 10° C. using a Haake VT550 viscometer @45 RPM. Theviscosity results are reported in Table 8a in centipoise.

TABLE 8a Lupasol SK (wt %) 480 g a.e./L dicamba 600 g a.e./L dicamba 0 — 20 1.5 — 105 2  55 — 3 — 280 4 160 460 5 — 700 6 335 — 8 650 — 8.5 770—

The data show that the viscosity of a formulation increases withincreasing amount of polymer and dicamba salt.

Example 9

The compatibility of MEA dicamba and tank mixes containing MEA dicambawith Roundup WeatherMAX® or Roundup PowerMAX® with the drift controlagents Gardian®, Gardian Plus®, Dri-Gard®, Pro-One XL™, Array™,Compadre™, In-Place®, Bronc® Max EDT, EDT Concentrate™, Coverage® andBronc® Plus Dry EDT was evaluated. Aqueous formulations were prepared asdescribed in Table 9a below where “Form” refers to the formulation,“Drift Cont.” refers to the drift control agent, “Amt” refers to theamount, “W.MAX” refers to ROUNDUP WEATHERMAX, and “P.MAX” refers toROUNDUP POWERMAX.

TABLE 9a Form. Drift Cont. Amt. Dicamba pH ROUNDUP 9A GARDIAN 0.75 mL0.52 g   — 6.2 9B GARDIAN PLUS 5 mL 0.52 g   — 6.72 9C DRI-GARD 1.44 g0.52 g   — 7.16 9D PRO-ONE XL 1.56 g 0.52 g   — 6.74 9E ARRAY 1.68 g0.52 g   — 7.25 W.MAX 9F GARDIAN 0.75 mL 1 g 3 g 5.13 9G GARDIAN PLUS 5mL 1 g 3 g 5.01 9H DRI-GARD 1.44 g 1 g 3 g 4.97 9I PRO-ONE XL 1.56 g 1 g3 g 4.98 9J ARRAY 1.68 g 1 g 3 g 4.96 9K COMPADRE 0.125 mL 1 g 3 g 5.119L IN PLACE 1.5 g 1 g 3 g 5.15 9M BRONC MAX 2 mL 1 g 3 g 5.14 EDT 9N EDT2 mL 1 g 3 g 5.18 CONCENTRATE 9O COVERAGE 3.1 mL 1 g 3 g 5.14 9P BRONCPLUS 2.4 g 1 g 3 g 5.12 DRY EDT 9Q GARDIAN 0.75 mL 2 g 6 g 5.03 9RGARDIAN PLUS 5 mL 2 g 6 g 4.97 9S DRI-GARD 1.44 g 2 g 6 g 4.94 9TPRO-ONE XL 1.56 g 2 g 6 g 4.96 9U ARRAY 1.68 g 2 g 6 g 5 9V COMPADRE0.125 mL 2 g 6 g 5.06 9W IN PLACE 1.5 g 2 g 6 g 5.13 9X BRONC MAX 2 mL 2g 6 g 5.1 EDT 9Y EDT 2 mL 2 g 6 g 5.08 CONCENTRATE 9Z COVERAGE 3.1 mL 2g 6 g 5.11 9AA BRONC PLUS 2.4 g 2 g 6 g 5.02 DRY EDT P.MAX 9BB GARDIAN0.75 mL 1 g 3 g 4.9 9CC GARDIAN PLUS 5 mL 1 g 3 g 4.84 9DD DRI-GARD 1.44g 1 g 3 g 4.82 9EE PRO-ONE XL 1.56 g 1 g 3 g 4.8 9FF ARRAY 1.68 g 1 g 3g 4.78 9GG COMPADRE 0.125 mL 1 g 3 g 4.86 9HH IN PLACE 1.5 g 1 g 3 g4.87 9II BRONC MAX 2 mL 1 g 3 g 4.95 EDT 9JJ EDT 2 mL 1 g 3 g 4.89CONCENTRATE 9KK COVERAGE 3.1 mL 1 g 3 g 4.93 9LL BRONC PLUS 2.4 g 1 g 3g 4.9 DRY EDT 9MM GARDIAN 0.75 mL 2 g 6 g 4.82 9NN GARDIAN PLUS 5 mL 2 g6 g 4.76 9OO DRI-GARD 1.44 g 2 g 6 g 4.75 9PP PRO-ONE XL 1.56 g 2 g 6 g4.75 9QQ ARRAY 1.68 g 2 g 6 g 4.76 9RR COMPADRE 0.125 mL 2 g 6 g 4.8 9SSIN PLACE 1.5 g 2 g 6 g 4.87 9TT BRONC MAX 2 mL 2 g 6 g 4.92 EDT 9UU EDT2 mL 2 g 6 g 4.9 CONCENTRATE 9VV COVERAGE 3.1 mL 2 g 6 g 4.88 9WW BRONCPLUS 2.4 g 2 g 6 g 4.86 DRY EDT

The Table 9a formulations were evaluated for compatibility by observingthe appearance after storage at room temperature after one hour. Afterone hour, the solutions were poured through a 150 micron sieve andobserved for the presence of solids. The results are reported in Table9b below.

TABLE 9b Form. Observations Separations 9A Clear None 9B Clear None 9CHazy White None 9D Hazy White None 9E Suspension that separates out in aUndissolved few hours particles 9F Clear None 9G Clear None 9H Hazy None9I Clear Undissolved particles 9J Suspension that separates out in a —few hours 9K Transparent blue-green solution None 9L Hazy light blue 1mm cream, 4 mm oil 9M Clear blue None 9N Clear blue None 9O Hazy lightblue 5 mm cream, 7 mm oil 9P Very hazy, light blue Undissolved particles9Q Clear None 9R Clear None 9S Hazy None 9T Dissolved better than with 3g W.MAX Undissolved particles 9U Suspension that separates out in a —few hours 9V Transparent blue-green solution None 9W Hazy light blue 3mm oil 9X Clear blue None 9Y Clear blue None 9Z Hazy light blue 1 mmcream, 6 mm oil 9AA Very hazy, light blue Undissolved particles 9BBClear None 9CC Clear None 9DD Hazy None 9EE Clear None 9FF Suspensionthat separates out in a — few hours 9GG Clear None 9HH Hazy White 4 mmoil 9II Clear None 9JJ Clear None 9KK Very hazy white 7 mm oil 9LL ClearUndissolved particles 9MM Clear None 9NN Clear None 9OO Hazy None 9PPClear None 9QQ Suspension that separates out in a — few hours 9RR ClearNone 9SS Hazy White 5 mm oil 9TT Clear None 9UU Clear None 9VV Very hazywhite 8 mm oil 9WW Clear Undissolved particles

GARDIAN, GARDIAN PLUS, COMPADRE, BRONC MAX EDT and EDT CONCENTRATE werecompatible with all of the mixtures and dicamba alone. Each createdclear solutions with no separation and left little to no particles on a150 um sieve. DRI-GARD dissolved well, but the solutions were all hazy.PRO-ONE XL did create clear solutions but some particles would notdissolve in the tests containing ROUNDUP WEATHER MAX. In all cases ARRAYappeared to suspend for a few hours, but precipitated with time leavinga large amount of residue on the Nessler tubes. IN-PLACE and COVERAGEcreated emulsions that separated quickly. BRONC PLUS DRY EDT did notdissolve completely.

PRO-ONE XL and BRONC PLUS MAX EDT were the only formulations to showclear differences in compatibility between ROUDNUP WEATHER MAX andROUNDUP POWER MAX. PRO-ONE XL dissolved better in ROUNDUP POWER MAX andBRONC PLUS MAX EDT created a clear solution with Power Max but created ahazy solution with ROUNDUP WEATHER MAX.

Example 10

The aqueous solubility of the various salts of dicamba prepared from thebases sodium, potassium, DGA, MEA and hexamethylene diamine (NMDA) saltof dicamba was measured. The maximum solubility was measured by taking asolution of that salt containing salt crystals and equilibrating thesolution at 20° C. and 0° C. for 5 to 7 days. The solution was thenpassed through a 0.45 micron filter and assayed by HPLC for solubledicamba. The results are reported in Table 10a below where “salt” refersto the dicamba salt, the solubility in reported in wt % acid equivalent(a.e.) and wt % active ingredient (a.i.).

TABLE 10a 20° C. 20° C. 0° C. 0° C. Salt a.e. a.i. a.e. a.i. Comments Na36.3 40.3 33 36.3 Crystals form easily K 54.6 64 52.7 61.8 Crystals formon surfaces easily DGA <50 — — — Crystals formed slowly MEA >71.9 >91.8— — No crystals, sticky oil HMDA 14.1 17.8 11.2 14.1 Pasty solid

The solutions of the MEA and DGA salts were found to be particularlydifficult to get to form crystals. The MEA salt solution did not formcrystals and it took several weeks for a DGA salt solution at ˜57% a.e.to start to form crystals. It should be noted that, when these saltsolutions dry on a glass surface, in some experiments a sticky residueis left that does not form crystals. In other experiments crystals didform upon drying MEA dicamba solutions. The data show that it can bedifficult to initiate crystal growth from MEA dicamba solutions.

The Na and K salts formed crystals very readily on a glass surface. Asthe solution dried, a powdery residue of salt formed quickly andreadily.

In a second experiment, the aqueous solubility of the sodium, potassium,DGA and MEA salts of dicamba and dicamba acid were measured at 20° C.was measured. The results are reported in Table 10b below:

TABLE 10b Dicamba wt % a.e. @20° C. wt % a.i. @20° C. acid 0.4 — sodiumsalt 36.3 40.3 potassium salt 54.6 64 DGA salt 56.5 83.4 MEA salt 66.184.4

Example 11

The compatibility of 480 and 600 g a.e./L solutions of MEA dicamba withvarious surfactants was evaluated as a function of cloud point. Theresults are reported in Table 11a below where “salt” refers to thedicamba salt, “wt % a.e.” refers to the dicamba concentration, “SurfConc” refers to the surfactant concentration and “Cld Pt” refers tocloud point. Formulations having a dicamba loading of 38.5-40 wt % a.e.contained about 480 g a.e./L dicamba and formulations having a dicambaloading of 48 wt % a.e. contained about 600 g a.e./L dicamba.

TABLE 11a Form. Salt wt % a.e. Surfactant Surf Conc Cld Pt 11A K 38.5Surf3 10 wt % >90° C. 11B K 38.5 Surf29 10 wt % >90° C. 11C MEA 38.5Surf3 10 wt % >90° C. 11D MEA 38.5 Surf29 10 wt % >90° C. 11E MEA 38.5Surf30 10 wt % >90° C. 11F MEA 38.5 Surf31 10 wt % >90° C. 11G MEA 38.5Surf32 10 wt % >90° C. 11H MEA 38.5 Surf33 10 wt % >90° C. 11I MEA 38.5Surf34 10 wt % >90° C. 11J K 38.5 Surf30 10 wt % >90° C. 11K K 38.5Surf31 10 wt % >90° C. 11L K 38.5 Surf32 10 wt % >90° C. 11M K 38.5Surf33 10 wt % >90° C. 11N K 38.5 Surf34 10 wt % >90° C. 11O K 38.5Surf35 10 wt % >90° C. 11P K 38.5 Surf5 10 wt % >90° C. 11Q MEA 38.5Surf35 10 wt % >90° C. 11R MEA 38.5 Surf5 10 wt % >90° C. 11S MEA 38.5Surf4 10 wt % >90° C. 11T K 38.5 Surf4 10 wt % >90° C. 11U MEA 38.5Surf36 0.8 wt %  >90° C. 11V MEA 38.5 Surf36 2.7 wt %  >90° C. 11W MEA38.5 Surf37 10 wt % >90° C. 11X K 38.5 Surf37 10 wt % >90° C. 11Y K 38.5Surf2 15 wt % >90° C. 11Z MEA 38.5 Surf2 15 wt % >90° C. 11AA MEA 38.5Surf40 10 wt % >90° C. 11BB MEA 48 Surf3 10 wt % >90° C. 11CC MEA 48Surf38 10 wt % >90° C. 11DD MEA 48 Surf1 10 wt % >90° C. 11EE MEA 48Surf36 1.5 wt %  >90° C. 11FF MEA 48 Surf34 10 wt % >90° C. 11GG MEA 48Surf39 10 wt % >90° C. 11HH MEA 48 Surf6 10 wt % >90° C. 11II MEA 48Surf2 10 wt % >90° C. 11JJ MEA 48 Surf4 10 wt % >90° C. 11KK MEA 40Surf5  8 wt % >90° C. 11LL MEA 48 Surf29 14 wt % >90° C.

It is demonstrated by this data that a wide range of different types ofsurfactants are surprisingly compatible with highly concentrated K andMEA salt solutions of dicamba.

Example 12

Aqueous tank mix compatibility of the Na, MEA and DGA dicamba salts withpotassium glyphosate was measured. A 35.8% a.e. aqueous solution of thedicamba salt solution was added to an aqueous solution comprising 7.7%Roundup POWERMAX® herbicide (containing 540 g a.e./L potassiumglyphosate) until precipitation was noted. The weight of the dicambasolution that caused precipitation was noted. The results are reportedin Table 12a below where “salt” refers to the dicamba salt and “g tocrystals” refers to the total amount of grams of dicamba a.e. that wererequired to induce crystallization or precipitation of crystals.

TABLE 12a Salt g to crystals Comment Na 13.6 — DGA >17 CLARITY - clearsolution with no precipitate MEA >34.2 Clear solution, no precipitate

Only the sodium salt induced crystallization in the presence ofpotassium glyphosate.

Formulation 11 BB was discovered to have low viscosity demonstratingthat a 600 g/L a.e. MEA dicamba formulation containing 10% surfactanthas a low viscosity and would be easily pumpable. The viscosity as afunction of temperature was measured and the results are reported inTable 12b below.

TABLE 12b Temp (° C.) Viscosity (cP) 2.5 201.4 6.5 161.5 10.5 127.1 14.699.7 18.3 79.4 22.1 63.7 26 52.2 29.8 42.7

Example 13

In certain formulations containing MEA dicamba and polyimine polymer,the polymer may precipitate upon dilution, particularly at low pH.Addition of APA surfactants to these formulations was evaluated todetermine if polyimine polymer dissolution could be facilitated.

A MEA dicamba solution was prepared by mixing together 799.9 grams (64%w/w/) dicamba acid, 198.6 grams (15.9% w/w) MEA and 251.4 grams (20.1%w/w) water until dissolved.

A 16.6% Lupasol P (Poly1) solution was prepared by mixing together 58.2grams (33.1% w/w) Lupasol P (50%) and 117.5 grams (66.9% w/w water)until dissolved.

Formulations of MEA dicamba containing Lupasol P, and Armeen APA 8, 10(Surf43) were prepared by combining, in order, the MEA dicamba solution,water, the Armeen APA, and the Lupasol P solution using the amountsreported in Table 13a.

TABLE 13a Form. MEA dicamba (g) Poly1 (g) Surf43 (g) Water (g) pH 13A33.33 12.52 0 4.17 9.26 13B 33.33 12.52 1 3.15 9.33 13C 33.33 12.52 1.52.65 9.35 13D 33.33 12.54 1.75 2.41 9.38 13E 33.33 12.55 2.01 2.17 9.4

In a series of evaluations, 1 mL of each of the Table 13a formulationswere combined with 2 mL ROUNDUP WEATHERMAX and 47 mL water in a 50 mLNessler tube. The results are reported in Table 13b.

TABLE 13b Form. Observation 13A Polymer settled to the bottom of thetube as white lumps 13B White lumps formed, a few settled to the bottomof the tube 13C White lumps formed then dissolved before settling tobottom 13D Very few white lumps formed then dissolved before settling tobottom 13E No lumps formed, dissolved well

The formulations containing APA surfactant showed little or noprecipitation of the polymer compared to formulations containing no APAsurfactant.

Aqueous formulations comprising MEA dicamba, Lupasol SK, and APAsurfactants were formulated as indicated in Table 13c wherein eachformulation contained 480 g a.e./L MEA dicamba, 4.15% a.i. Lupasol SKand 2% APA surfactant.

TABLE 13c Formulation APA 681K7H Surf41 682M3D Surf42 683Q9L Surf43684V5F Surf44 685Y4N Surf45 686X8I Surf46 687E1R Surf47

For all of the formulations studied, the addition of APA surfactantfacilitated dissolution of the polymer and no precipitation upondilution with water or in ROUNDUP tank mixtures was observed.

Additional formulations with varied concentrations of APA wereevaluated. Data is provided in Table 13d wherein each formulation was480 g a.e./L MEA dicamba and 4.15% a.i. Lupasol SK.

TABLE 13d Formulation wt % Surf43 521O5B 0.50% 522C2A 1.00% 523M9I 3.00%524R0P 4.00% 525L2Z   5%

For all of the formulations studied, the addition of APA facilitateddissolution of the polymer and no precipitation upon dilution with wateror in ROUNDUP tank mixtures was observed.

Cold temperature stability of aqueous MEA dicamba formulationscontaining APA was evaluated. The formulation of the MEA dicamba/APAformulations and test results are provided in Table 13e where allformulations contain 4.15% a.i. Lupasol SK and 2% APA.

TABLE 13e % Dicamba Form. (a.e.) Polymer APA −25° C. −20° C. −15° C.091U6J 36.00% None none Frozen Frozen Liquid 033P3X 36.00% Poly5 NoneLiquid Liquid Liquid 048L8N 36.50% Poly5 Surf43 Frozen Frozen Liquid684M1S 36.30% Poly5 Surf45 Frozen Liquid Liquid 686T6G  36.3% Poly5Surf47 Frozen Frozen Liquid

An experiment was performed to evaluate the efficacy of applicationmixtures comprising MEA dicamba, polyimine polymer and APA. Theformulations of the experimental dicamba formulations are indicated intable 13f where the dicamba concentration is reported as wt % a.e. andthe concentration of the other components in wt % is indicated inparentheses.

TABLE 13f % MEA dicamba Form. a.e. by wt Poly.(%) APA 810B4B 39.5 Poly1(4.15) Surf43 (2) 810D3E 39.5 Poly1 (4.15) Surf45 (2) 810F9K 39.5 Poly1(4.15) Surf47 (2) 751W4I 36.3 Poly5 (4) Surf45 (2) 752A4J 36.3 Poly5 (4)Surf47 (2) 811U3Y 36.3 Poly3 (4) Surf43 (2) 812T5F 36.3 Poly3 (4) Surf45(2)

The formulations from Table 13f, CLARITY and 925S3J were sprayed overthe top of 10-15 cm velvetleaf (ABUTH) plants to evaluate herbicidalefficacy at application rates of 140, 280, and 561 g a.e./ha. Herbicidalefficacy was evaluated 21 days after treatment. The data is presented inTable 13g in an ANOVA summary of formulations mean comparisons by rate.

TABLE 13g Form. 140 g a.e./ha 280 g a.e/ha 560 g a.e/ha CLARITY 44.270.8 85.0 925S3J 57.5 80.0 90.0 810B4B 50.0 74.2 84.2 810D3E 58.3 82.586.7 810F9K 64.4 74.2 86.7 751W4I 56.7 83.3 91.7 752A4J 65.8 81.7 88.3811U3Y 50.0 80.0 87.5 812T5F 61.7 75.0 90.8

At the 140 g a.e./ha application rate 925S3J, 810D3E, 810F9K, 751W4I,752A4J, and 812T5F were more efficacious than CLARITY. At the 280 ga.e./ha application rate 925S3J, 810D3E, 751W4I, 752A4J, and 811U3Y weremore efficacious than CLARITY. At the 560 g a.e./ha application rate925S3J, 751W4I and 811U3Y were more efficacious than CLARITY.

The volatility of formulations comprising MEA dicamba, polyiminepolymer, and APA was measured and the results are shown in Table 13hbelow.

TABLE 13h % Dicamba Form. Polymer Dicamba APA pH ng/L 357C8D Poly1(1.25) 10 Surf43 (4) 6.98 0.413 358X5Y Poly1 (1.25) 10 Surf43 (4) 8.000.321 359R8Y Poly1 (1.25) 10 Surf43 (4) 9.02 0.051 360L4F Poly1 (1.25)10 Surf45 (2) 7.14 0.052 361M0G Poly1 (1.25) 10 Surf45 (2) 8.04 0.056362W7S Poly1 (1.25) 10 Surf45 (2) 9.21 0.049 475K3N Poly3 (1.25) 10Surf45 (4) 7.07 0.459 476I8K Poly3 (1.25) 10 Surf45 (4) 8.04 0.215477E9B Poly3 (1.25) 10 Surf45 (4) 9.03 0.039

Addition of 2% ACAR 7051 to the formulation comprising MEA dicamba andpolyimine polymer greatly reduced dicamba volatility at all 3 pH valuesof 7.14, 8.04 and 9.21 while addition of 4% Armeen APA 810 showedsignificant reduction in volatility at pH 9.02.

Example 14

The volatility of MEA dicamba formulations containing polyimine polymerwith ROUNDUP herbicides was evaluated and compared with CLARITY+ROUNDUPcombination. The dicamba formulations were mixed with ROUNDUP POWERMAXto give a 1:1 ratio of dicamba to glyphosate. The results are shown inTable 14a.

TABLE 14a Form. Dicamba Form. pH Polymer Volatility (ng/L) 114L6HCLARITY 4.57 none 3.172 112Q1E MEA DICAMBA 4.55 none 5.729 115D5B MEADICAMBA 5.22 Poly2 1.758

The dicamba formulation containing the polyimine polymer had reducedvolatility compared to both MEA dicamba and CLARITY formulations.

In a further set of experiments, the volatility of aqueous tank mixturescontaining dicamba salt and Roundup POWERMAX® was measured. Aqueousformulations were prepared as described in table 14b. The tank mixtureswere evaluated for dicamba concentration in the gas phase (air) throughair sampling while being exposed to constant temperature and humidity inhumidome in growth chambers.

Humidomes were purchased from Hummert International (Part Nos 14-3850-2for humidomes and 11-3050-1 for 1020 flat tray) and modified by cuttinga 2.2 centimeter (cm) diameter hole on one end approx 5 cm from the topto allow for insertion of glass air sampling tube (22 mm OD) containinga polyurethane foam (PUF) filter. The sampling tube was secured with aViton o-ring on each side of the humidome wall. The air sampling tubeexternal to the humidome was fitted with tubing that was connected to avacuum manifold immediately prior to sampling.

Formulations containing dicamba were introduced into the humidome in oneof two ways. Solutions containing dicamba formulations (20 mL) wereplaced in a petri dish which was positioned on the flat tray beneath thehumidome. Alternatively, the flat tray beneath the humidome was filled 1liter of sifted dry or wet 50/50 soil (50% Redi-Earth and 50% US 10Field Soil) to a depth of about 1 cm and dicamba formulations weresprayed over the soil using a track sprayer at a rate of 10 gallons peracre (GPA). To avoid contamination of the sides of the flat tray eachtray was nested in an empty tray prior to spraying. In some evaluations,potted soybean or velvetleaf plants were placed on top of the soil.

The flat tray bottom containing the dicamba formulation in a petri dishor on soil was covered with a humidome lid and the lid was secured withclamps. The assembled humidomes were placed in a temperature andhumidity controlled environment and connected to a vacuum manifoldthrough the air sampling line. Air was drawn through the humidome andPUF at a rate of 2 liters per minutes (LPM) for 24 hours at which pointthe air sampling was stopped. The humidomes were then removed from thecontrolled environment and the PUF filter was removed. The PUF filterwas extracted with 20 mL of methanol and the solution was analyzed fordicamba concentration using liquid chromatography-mass spectroscopymethods known in the art. The reported results are an average of 3-6samples.

Aqueous formulations were prepared as indicated in Table 14b below andhumidome results are indicated in Table 14c below. Each formulationcontained a combination of the indicated dicamba formulation andPOWERMAX and having concentrations of 0.5 wt % a.e. dicamba and 1.5 wt %a.e. glyphosate. In Table 14b, “Form. No.” refers to formulation numberand “Dicamba form.” refers to dicamba formulation. In Table 14c, “T”refers to temperature in degrees centigrade, “RH” refers to relativehumidity, “SD” refers to standard deviation, “ng/L” refers to the airsample dicamba concentration in nanograms per liter, “Petri” refers topetri dish, “soil” refers to 50/50 soil (50% Redi-Earth and 50% US 10Field Soil), “soy” refers to soybean and “vel” refers to velvetleaf.

TABLE 14b Form No. Dicamba form. Dicamba salt pH 14(1) CLARITY DGA 4.4614(2) BANVEL DMA 4.47 14(3) 968Q3W MEA 4.5 14(4) 933C3S MEA 4.81

TABLE 14c Form. Dicamba No. Medium Plant T RH ng/L SD % plant injury14(1) Petri None 35 40 0.179 0.03 14(2) Petri None 35 40 0.151 0.02114(3) Petri None 35 40 0.209 0.057 14(4) Petri None 35 40 0.165 0.02514(1) Petri Soy 35 40 0.115 0.045 18% 10 DAT 14(2) Petri Soy 35 40 0.2020.084 19% 10 DAT 14(3) Petri Soy 35 40 0.071 0.02 20% 10 DAT 14(4) PetriSoy 35 40 0.056 0.018 18% 10 DAT 14(1) Soil Soy 35 40 1.254 0.145 32% 13DAT 14(2) Soil Soy 35 40 2.851 1.258 41% 13 DAT 14(3) Soil Soy 35 401.308 0.044 37% 13 DAT 14(4) Soil Soy 35 40 1.139 0.073 34% 13 DAT 14(1)Soil Vel 27 40 0.384 0.162 37% 14 DAT 14(2) Soil Vel 27 40 0.594 0.20837% 14 DAT 14(3) Soil Vel 27 40 0.462 0.154 37% 14 DAT 14(4) Soil Vel 2740 0.228 0.097 36% 14 DAT 14(1) Soil Vel 27 40 0.487 0.198 16% 14 DAT14(2) Soil Vel 27 40 0.697 0.183 19% 14 DAT 14(3) Soil Vel 27 40 0.6490.283 18% 14 DAT 14(4) Soil Vel 27 40 0.302 0.103 13% 14 DAT

The data in Table 14c indicates that composition 968Q3W (containing MEAdicamba) and BANVEL showed the highest volatility in this humidome test.933C3S (containing MEA dicamba and Lupasol SK polymer) showed the lowestvolatility. Plant injury data was inconclusive in this test.

In a second set of humidome experiments, aqueous formulations wereprepared as indicated in Table 14d below. Each formulation contained acombination of the indicated dicamba formulation and POWERMAX and havingconcentrations of 1 wt % a.e. dicamba and 3 wt % a.e. In Table 14d,“Form. No.” refers to formulation number and “Dicamba form.” refers todicamba formulation. In Table 14e, “T” refers to temperature in degreescentigrade, “RH” refers to relative humidity, “SD” refers to standarddeviation, “ng/L” refers to the air sample dicamba concentration innanograms per liter, “soil” refers to 50/50 soil (50% Redi-Earth and 50%US 10 Field Soil) wherein the compositions are applied to the soil, “RRsoy” refers to ROUNDUP READY soybean wherein the compositions areapplied to the plant canopy, and “DT soy” refers to dicamba tolerantsoybean wherein the compositions are applied to the plant canopy.

TABLE 14d Form No. Dicamba form. Dicamba salt pH 14(5) CLARITY DGA 4.4114(6) 968Q3W MEA 4.43 14(7) 944L8M DGA 4.48 14(8) 933C3S MEA 4.81

TABLE 14e Form. No. Medium T RH Dicamba ng/L SD 14(5) Soil 27 40 0.4090.142 14(6) Soil 27 40 0.632 0.186 14(5) RR soy 27 40 0.77 0.194 14(6)RR soy 27 40 0.822 0.347 14(5) DT soy 27 40 0.619 0.112 14(6) DT soy 2740 0.837 0.144 14(7) Soil 27 40 0.265 0.077 14(8) Soil 27 40 0.178 0.06214(7) RR soy 27 40 0.468 0.081 14(8) RR soy 27 40 0.464 0.117

The data show that the addition of PEI polymer to MEA dicambaformulations reduces the volatility of dicamba from a canopy of ROUNDUPREADY soybeans and from a canopy of dicamba tolerant soybeans.

In a set of tube test experiments, aqueous formulations were prepared asindicated in Table 14f below. In Table 14f, “Form. No.” refers toformulation number and “Dicamba form.” refers to dicamba formulation.Each Table 14f formulation contained 2 wt % a.e. dicamba and 6 wt % a.e.glyphosate. Glyphosate “K salt” refers to the potassium salt ofglyphosate wherein the glyphosate source was an aqueous solutioncontaining 47.9 wt % a.e. potassium glyphosate; POWERMAX refers toROUNDUP POWERMAX®; and WEATERMAX refers to ROUNDUP WEATHERMAX®. In Table14g, “SD” refers to standard deviation and “ng/L” refers to the airsample dicamba concentration in nanograms per liter.

TABLE 14f Form. No. Dicmaba Form. Dicamba Salt Additional componentsGlyphosate 14(9) BANVEL DMA — K salt 14(10) 957Y2S MEA — K salt 14(11)CLARITY DGA — K salt 14(12) 929P6H MEA — K salt 14(13) 931F5L MEA — Ksalt 14(14) MEA-Dicamba MEA 0.2% LUPASOL P + K salt Surf48 14(15)CLARITY DGA 0.2% LUPASOL P K salt 14(16) MEA-Dicamba MEA 0.2% LUPASOL HFK salt 14(17) MEA-Dicamba MEA 0.2% LUPASOL P + K salt AGM 550 14(18)MEA-Dicamba MEA 0.2% LUPASOL FG + K salt Surf3 14(19) CLARITY DGA —POWERMAX 14(20) 931F5L MEA — POWERMAX 14(21) 926Y7O MEA Surf2 K salt14(22) 925S3J MEA Surf48 K salt 14(23) 956N5T MEA Surf3 K salt 14(24)CLARITY DGA 0.2% LUPASOL SK K salt 14(25) CLARITY DGA 0.2% LUPASOL HF Ksalt 14(26) CLARITY DGA 0.2% LUPASOL FG K salt 14(27) 933C3S MEA — Ksalt 14(28) DEA dicamba salt DEA — K salt solution 14(29) K-Dicamba K0.2% LUPASOL SK K salt 14(30) K-Dicamba K 0.2% LUPASOL P K salt 14(31)K-Dicamba K 0.2% LUPASOL HF K salt 14(32) K-Dicamba K 0.2% LUPASOL FG Ksalt 14(33) MEA-Dicamba MEA 0.05% LUPASOL SK + K salt 0.15% LUPASOL P14(34) MEA-Dicamba MEA 0.15% LUPASOL SK + K salt 0.05% LUPASOL P 14(35)Na-Dicamba Na — K salt 14(36) Na-Dicamba Na — POWERMAX 14(37) BANVEL DMA0.2% LUPASOL SK K salt 14(38) BANVEL DMA 0.2% LUPASOL P K salt 14(39)BANVEL DMA 0.2% LUPASOL HF K salt 14(40) BANVEL DMA 0.2% LUPASOL FG Ksalt 14(41) MEA-Dicamba MEA 0.15% LUPASOL FG K salt 14(42) MEA-DicambaMEA 0.10% LUPASOL FG K salt 14(43) MEA-Dicamba MEA 0.05% LUPASOL FG Ksalt 14(44) MEA-Dicamba MEA 0.05% LUPASOL P + K salt 0.05% LUPASOL HF14(45) MEA-Dicamba MEA 0.05% LUPASOL P + K salt 0.05% LUPASOL PN6014(46) MEA-Dicamba MEA 0.05% LUPASOL P + K salt 0.05% LUPASOL FG 14(47)MEA-Dicamba MEA 0.05% LUPASOL SK + K salt 0.05% LUPASOL FG 14(48)MEA-Dicamba MEA 0.05% LUPASOL SK + K salt 0.05% LUPASOL HF 14(49)MEA-Dicamba MEA 0.05% LUPASOL SK + K salt 0.05% LUPASOL PN60 14(50)MEA-Dicamba MEA 0.05% LUPASOL FG + K salt 0.05% LUPASOL HF 14(51)MEA-Dicamba MEA 0.05% LUPASOL FG + K salt 0.05% LUPASOL PN60 14(52)MEA-Dicamba MEA 0.05% LUPASOL HF + K salt 0.05% LUPASOL PN60 14(53)K-Dicamba K 0.05% LUPASOL P + K salt 0.05% LUPASOL SK 14(54) K-Dicamba K0.05% LUPASOL P + K salt 0.05% LUPASOL HF 14(55) K-Dicamba K 0.05%LUPASOL P + K salt 0.05% LUPASOL PN60 14(56) K-Dicamba K 0.05% LUPASOLP + K salt 0.05% LUPASOL FG 14(57) K-Dicamba K 0.05% LUPASOL SK + K salt0.05% LUPASOL FG 14(58) K-Dicamba K 0.05% LUPASOL SK + K salt 0.05%LUPASOL HF 14(59) K-Dicamba K 0.05% LUPASOL SK + K salt 0.05% LUPASOLPN60 14(60) K-Dicamba K 0.05% LUPASOL FG + K salt 0.05% LUPASOL HF14(61) K-Dicamba K 0.05% LUPASOL FG + K salt 0.05% LUPASOL PN60 14(62)K-Dicamba K 0.05% LUPASOL HF + K salt 0.05% LUPASOL PN60 14(63)MEA-Dicamba MEA 0.10% LUPASOL FG K salt 14(64) MEA-Dicamba MEA 0.15%LUPASOL FG K salt 14(65) MEA-Dicamba MEA 0.21% LUPASOL FG K salt 14(66)MEA-Dicamba MEA 0.25% LUPASOL FG K salt 14(67) MEA-Dicamba MEA 0.30%LUPASOL FG K salt 14(68) MEA-Dicamba MEA 0.41% Surf30 K salt 14(69)MEA-Dicamba MEA 0.05% LUPASOL HF K salt 14(70) MEA-Dicamba MEA 0.10%LUPASOL HF K salt 14(71) MEA-Dicamba MEA 0.15% LUPASOL HF K salt 14(72)MEA-Dicamba MEA 0.20% LUPASOL HF K salt 14(73) MEA-Dicamba MEA 0.25%LUPASOL HF K salt 14(74) MEA-Dicamba MEA 0.30% LUPASOL HF K salt 14(75)MEA-Dicamba MEA 0.05% LUPASOL P K salt 14(76) MEA-Dicamba MEA 0.10%LUPASOL P K salt 14(77) MEA-Dicamba MEA 0.15% LUPASOL P K salt 14(78)MEA-Dicamba MEA 0.20% LUPASOL P K salt 14(79) MEA-Dicamba MEA 0.25%LUPASOL P K salt 14(80) MEA-Dicamba MEA 0.30% LUPASOL P K salt 14(81)K-Dicamba K 0.05% LUPASOL HF K salt 14(82) K-Dicamba K 0.10% LUPASOL HFK salt 14(83) K-Dicamba K 0.15% LUPASOL HF K salt 14(84) K-Dicamba K0.20% LUPASOL HF K salt 14(85) K-Dicamba K 0.25% LUPASOL HF K salt14(86) K-Dicamba K 0.30% LUPASOL HF K salt 14(87) K-Dicamba K 0.05%LUPASOL FG K salt 14(88) K-Dicamba K 0.10% LUPASOL FG K salt 14(89)K-Dicamba K 0.15% LUPASOL FG K salt 14(90) K-Dicamba K 0.20% LUPASOL FGK salt 14(91) K-Dicamba K 0.25% LUPASOL FG K salt 14(92) K-Dicamba K0.30% LUPASOL FG K salt 14(93) MEA-Dicamba MEA 0.15% LUPASOL FG POWERMAX14(94) MEA-Dicamba MEA 0.20% LUPASOL FG POWERMAX 14(95) 942T3R DGA — Ksalt 14(96) K-Dicamba K 0.20% LUPASOL FG K salt 14(97) MEA-Dicamba MEA0.25% LUPASOL FG POWERMAX 14(98) 942T3R DGA — POWERMAX 14(99) 942T3R DGA— WEATHERMAX 14(100) 957Y2S MEA — WEATHERMAX 14(101) BANVEL DMA —POWERMAX 14(102) MEA-Dicamba MEA 0.2% LUPASOL FG + K salt Surf3 14(103)933C3S MEA — POWERMAX 14(104) DGA-Dicamba DGA 0.05% LUPASOL FG K salt14(105) DGA-Dicamba DGA 0.10% LUPASOL FG K salt 14(106) DGA-Dicamba DGA0.15% LUPASOL FG K salt 14(107) DGA-Dicamba DGA 0.20% LUPASOL FG K salt14(108) DGA-Dicamba DGA 0.25% LUPASOL FG K salt 14(109) DGA-Dicamba DGA0.30% LUPASOL FG K salt 14(110) DGA-Dicamba DGA 0.20% LUPASOL SK K salt14(111) DGA-Dicamba DGA 0.20% LUPASOL P K salt 14(112) DGA-Dicamba DGA0.20% LUPASOL HF K salt 14(113) MEA-Dicamba MEA 0.20% LUPASOL G20 K salt14(114) MEA-Dicamba MEA 0.20% LUPASOL G35 K salt 14(115) MEA-Dicamba MEA0.20% LUPASOL G100 K salt 14(116) DGA-Dicamba DGA 0.20% LUPASOL G20 Ksalt 14(117) DGA-Dicamba DGA 0.20% LUPASOL G35 K salt 14(118)DGA-Dicamba DGA 0.20% LUPASOL G100 K salt

TABLE 14g Form. No. pH Dicamba ng/L SD 14(9) 4.08 5.04 0.963 14(10) 4.083.052 0.682 14(11) 4.07 2.778 0.476 14(12) 4.19 2.801 0.039 14(13) 4.463.483 0.336 14(14) 4.47 3.397 0.199 14(15) 4.56 1.706 0.233 14(16) 4.512.622 0.113 14(17) 4.52 3.53 0.181 14(18) 4.1 3.949 1.342 14(19) 4.361.811 0.13 14(20) 4.65 1.766 0.329 14(21) 4.21 5.761 1.294 14(22) 4.233.566 0.184 14(23) 4.28 3.644 0.283 14(24) 4.22 2.218 0.589 14(25) 4.691.7 0.015 14(26) 4.64 1.08 0.184 14(27) 4.58 0.781 0.092 14(28) 4.12.398 0.592 14(29) 4.26 2.484 0.427 14(30) 4.54 2.454 0.531 14(31) 4.531.527 0.085 14(32) 4.49 1.152 0.194 14(33) 4.46 3.244 1.016 14(34) 4.353.176 0.153 14(35) 4.75 0.98 0.245 14(36) 4.87 1.566 0.451 14(37) 4.152.685 0.45 14(38) 4.46 3.611 0.732 14(39) 4.47 3.54 0.681 14(40) 4.481.879 0.045 14(41) 4.32 2.934 0.671 14(42) 4.26 2.965 0.392 14(43) 4.233.416 0.591 14(44) 4.31 4.482 0.912 14(45) 4.22 5.322 1.191 14(46) 4.293.052 0.492 14(47) 4.26 2.96 0.523 14(48) 4.23 4.978 1.258 14(49) 4.155.453 0.981 14(50) 4.31 2.513 0.709 14(51) 4.19 2.261 0.363 14(52) 4.213.605 0.888 14(53) 4.28 3.59 1.143 14(54) 4.35 3.599 0.788 14(55) 4.213.459 1.033 14(56) 4.27 2.483 0.63 14(57) 4.24 2.359 0.268 14(58) 4.232.545 0.543 14(59) 4.13 4.832 0.31 14(60) 4.34 2.761 0.801 14(61) 4.232.962 0.709 14(62) 4.2 2.622 0.609 14(63) 4.26 2.266 0.459 14(64) 4.322.51 0.41 14(65) 4.56 0.933 0.351 14(66) 4.56 1.323 0.407 14(67) 4.660.898 0.188 14(68) 4.25 3.564 0.337 14(69) 4.15 3.797 0.883 14(70) 4.273.953 0.702 14(71) 4.33 3.551 0.236 14(72) 4.44 2.641 0.863 14(73) 4.513.228 0.54 14(74) 4.63 2.776 0.386 14(75) 4.26 2.963 0.422 14(76) 4.342.829 0.868 14(77) 4.43 2.471 0.611 14(78) 4.53 2.156 0.573 14(79) 4.593.311 0.104 14(80) 4.67 2.451 0.173 14(81) 4.19 4.159 0.411 14(82) 4.283.417 0.487 14(83) 4.37 3.244 0.565 14(84) 4.44 3.431 0.998 14(85) 4.492.972 0.676 14(86) 4.54 2.515 0.739 14(87) 4.24 2.28 0.233 14(88) 4.331.91 0.458 14(89) 4.41 1.708 0.346 14(90) 4.52 0.908 0.631 14(91) 4.581.146 0.207 14(92) 4.64 1.094 0.232 14(93) 4.68 1.799 0.754 14(94) 4.712.412 0.84 14(95) 4.12 1.806 0.313 14(96) 4.52 1.457 0.371 14(97) 4.771.251 0.38 14(98) 4.41 1.688 0.197 14(99) 4.52 1.558 0.413 14(100) 4.4492.347 0.457 14(101) 4.34 3.898 0.991 14(102) 4.58 3.837 0.475 14(103)4.61 1.391 0.087 14(104) 4.25 1.972 0.343 14(105) 4.35 1.334 0.13514(106) 4.43 1.334 0.25 14(107) 4.53 1.431 0.373 14(108) 4.59 1.0460.097 14(109) 4.63 1.149 0.394 14(110) 4.18 3.551 0.241 14(111) 4.461.947 0.268 14(112) 4.45 2.725 0.634 14(113) 4.57 1.275 0.262 14(114)4.56 1.467 0.372 14(115) 4.53 2.797 0.936 14(116) 4.56 1.164 0.36414(117) 4.55 1.036 0.169 14(118) 4.54 1.34 0.204

The Table 14g data show that the addition of PEI reduces the volatilityof CLARITY (DGA dicamba), BANVEL (DMA dicamba) and potassium dicambawith LUPASOL FG providing the largest reduction. The data further showthat lower molecular weight LUPASOL PEIs provide the greatest volatilityreduction for MEA dicamba. The data further show that a weight ratio ofdicamba a.e. to PEI polymer of about 10:1 provides the best volatilityreduction. The data still further show that PEI polymers having amolecular weight in excess of about 5,000 Daltons are preferred.

Example 15

The spray droplet particle size of compositions of the present inventionand comparative compositions were measured using an Aerometrics phasedoppler particle analysis (PDPA) system. The samples were each dilutedin 15 L tap water at 20.0° C. to a final equivalent kilogram per hectare(kg/ha) value based on an application rate of 93 liters per hectare(L/ha). The kg/ha values are disclosed in Table 15a below. For eachreported kg/ha value, a corresponding concentration in grams acidequivalent per liter can be calculated from the application rate of 93L/ha. In particular, values of 0.073, 0.09, 0.28 and 0.56 kg/ha reportedin table 15a below correspond to 0.78, 0.97, 3 and 6 g a.e./L,respectively. Where the drift control agents GARDIAN and INTERLOCK areindicated, the concentration is reported in % v/v based on the finaldiluted formulation.

TABLE 15a Formulation Sample 1 Sample 2 Sample 3 Sample 4 CLARITY 0.0730.28 0.56 — CLARITY + 0.073 + 0.28 + — — GARDIAN 0.5% v/v 0.5% v/vCLARITY + 0.073 + 0.28 + — — INTERLOCK 0.3% v/v 0.3% v/v 962P0H 0.0730.28 0.56 — 962P0H + 0.070 + 0.28 + — — GARDIAN 0.5% v/v 0.5% v/v962P0H + 0.073 + 0.28 + — — INTERLOCK 0.3% v/v 0.3% v/v 908D1S 0.0730.28 0.56 — 908DIS + 0.073 + — — — GARDIAN 0.5% v/v 908DIS + 0.073 + — —— INTERLOCK 0.3% v/v 929P6H 0.073 0.28 0.56 — 929P6H + 0.073 + — — —GARDIAN 0.5% v/v 926Y7O 0.073 0.09 0.28 0.56 926Y7O + — 0.09 + 0.28 + —GARDIAN 0.5% v/v 0.5% v/v 926Y7O + 0.073 + — 0.28 + — INTERLOCK 0.3% v/v0.3% v/v 931F5L — 0.28 0.56 — 931F5L + — 0.28 + — — GARDIAN 0.5% v/v931F5L + — 0.28 + — — INTERLOCK 0.3% v/v GARDIAN 0.5% v/v — — —INTERLOCK 0.3% v/v — — —

Each mixture was sprayed through a Teejet XR8003VS nozzle tip at 276 kPa(40 psi) at a height of 30 cm above the probe volume of the AerometricsPDPA laser system. The size range scanned was from 25.7 μm-900.0 μm. Thevoltage for the photo-multiplier tube (PMT) was set to 325V.

Two types of measurement were made for each treatment: a stationarycenter measurement under the x-y axes intersection point (center); and ascan down the length of the long x-axis to yield an overall globalsample (x-scan). Each measurement was replicated 3 times. Thesereplicates were merged to yield an overall sample. This data was runthrough a macro program to generate data including (i) average velocity(in meters per second for the entire spray cloud); (ii) D10 (arithmeticmean diameter); (iii) D20 (area mean); (iv) D30 (volume mean); (v) D32(sauter mean); (vi) 10% and 90% points (The droplet particle size belowwhich 10% (or 90%) of the volume of the measured particles lie); (vii)Volume Median Diameter (Dv0.5—The droplet particle size below which 50%of the volume of particles are contained); (viii) Number Median Diameter(NMD—The particle size below which 50% of the number of dropletparticles are contained); (ix) relative span [(90% point−10% point)/VMD,wherein, the smaller the number, the more narrow (monodispersed) thedistribution]; (x) percent by volume and number <100 and <150 μm (theproportion of the volume of the spray cloud/number of droplet particlescontained within (above/below) a given size range); and (xi) percentdistributions by volume and number for 100-200 μm.

The PDPA particle size data for a first set of experiments is reportedin Table 15b below.

TABLE 15b % V <100 % V <150 % V 100 μm Formulation Measurement μm μm to200 μm Water Center 7.73 16.69 19.91 x-scan 4.32 12.02 18.75 CLARITYCenter 8.11 17.49 20.54 Sample 1 x-scan 4.78 12.62 18.89 CLARITY Center8.39 17.92 21.16 Sample 2 x-scan 4.44 12.19 18.87 CLARITY Center 9.3219.21 21.7 Sample 3 x-scan 5.3 13.73 20.24 926Y7O Center 5.16 13.2219.47 Sample 1 x-scan 2.99 9.79 17.03 926Y7O Center 4.66 12.19 18.42Sample 3 x-scan 2.84 9.12 16.15 926Y7O Center 6.11 14.82 20.32 Sample 4x-scan 3.44 10.47 17.66 926Y7O + Center 6.94 15.47 17.75 GARDIAN x-scan3.29 8.5 12.13 Sample 3 926Y7O + Center 2.49 8.15 15.18 INTERLOCK x-scan2.14 7.71 15.05 Sample 3 931F5L Center 5.33 13.41 19.19 Sample 2 x-scan2.91 9.39 16.43 931F5L Center 3.69 10.54 17.23 Sample 3 x-scan 2.42 8.2815.61 931F5L + Center 5.4 11.73 13.96 GARDIAN x-scan 2.47 6.43 9.45Sample 2 931F5L + Center 1.42 5.63 12.12 INTERLOCK x-scan 1.39 5.74 12.5Sample 2

The x-scan results for water, CLARITY Sample 3, 926Y7O Sample 4, 931F5LSample 3, 908D1S Sample 3 and 929P6H Sample 3 are depicted in FIG. 1.

Analysis of the Table 15b results show that the CLARITY prior artcompositions had a greater volume percent at less than 100 μm, less than150 μm and from 100 μm to 200 μm than each composition of the presentinvention at comparative dicamba concentrations thereby indicating thatthe inventive compositions provide a larger average droplet particlesize than the comparative prior art compositions.

The PDPA particle size data for a second set of experiments is reportedin Table 15c below wherein the dicamba final kg/ha values forformulation 926Y7O Samples 5, 6 and 7 were 0.072, 0.35 and 0.7 kg/ha,respectively.

TABLE 15c % V <100 % V <150 % V 100 μm Formulation Measurement μm μm to200 μm Water x-scan 4.7 12.78 19.5 Water + x-scan 2.76 7.38 10.91GARDIAN CLARITY x-scan 4.78 12.62 18.89 Sample 1 CLARITY x-scan 4.4412.19 18.87 Sample 2 CLARITY x-scan 5.3 13.73 20.24 Sample 3 CLARITY +x-scan 2.28 6.08 9.07 GARDIAN Sample 1 CLARITY + x-scan 1.78 6.73 13.44INTERLOCK Sample 1 962P0H x-scan 4.66 12.42 18.87 Sample 1 962P0H x-scan4.45 12.5 19.13 Sample 2 962P0H x-scan 4.4 12.44 19.38 Sample 3 962P0H +x-scan 2.46 6.36 9.2 GARDIAN Sample 1 962P0H + x-scan 1.65 6.44 13.58INTERLOCK Sample 1 908D1S x-scan 4.23 11.82 18.32 Sample 1 908D1S x-scan5.19 13.59 19.81 Sample 2 908D1S x-scan 6.26 15.68 22.05 Sample 3908D1S + x-scan 2.86 7.41 10.59 GARDIAN Sample 1 908D1S + x-scan 1.55.89 12.69 INTERLOCK Sample 1 929P6H x-scan 4.67 12.46 18.72 Sample 1929P6H x-scan 4.24 11.76 18.23 Sample 2 929P6H x-scan 4.31 11.72 18.04Sample 3 929P6H + x-scan 2.22 5.84 8.68 GARDIAN Sample 1 926Y7O x-scan3.46 10.7 17.71 Sample 5 926Y7O x-scan 2.69 8.9 16.6 Sample 6 926Y7Ox-scan 5.59 14.58 21.05 Sample 7 926Y7O + x-scan 2.63 7.09 10.44 GARDIANSample 2

Analysis of the Table 15c results show that the CLARITY prior artcompositions had a greater volume percent: at less than 100 μm, lessthan 150 μm and from 100 μm to 200 μm than each of compositions 962P0HSample 1, 908D1S Sample 1, 908D1S+INTERLOCK Sample 1, 929P6H Samples1-3, 929P6H+GUARDIAN Sample 1 and 926Y7O Sample 5 of the presentinvention at comparative dicamba concentrations; at less than 100 μm andfrom 100 μm to 200 μm than 962P0H Sample 3 at a comparative dicambaconcentration; at less than 100 μm and at less than 150 μm than962P0H+INTERLOCK Sample 1 at a comparative dicamba concentration; and atless than 150 μm and from 100 μm to 200 μm than composition 908D1SSample 3 at a comparative dicamba concentration thereby indicating thatthose inventive compositions provide a larger average droplet particlesize than the comparative prior art compositions.

The Average velocity (m/sec), NMD (in μm) and span for the measurementsreported in Table 15c are reported in Table 15d below.

TABLE 15d Average velocity NMD Formulation (m/sec) (μm) Span Water 5.5576.97 1.22 Water + 5.6 73.14 1.02 GARDIAN CLARITY 5.58 73.14 1.14 Sample1 CLARITY 5.78 79.33 1.18 Sample 2 CLARITY 5.58 71.77 1.18 Sample 3CLARITY + 5.69 72.47 0.97 GARDIAN Sample 1 CLARITY + 7.3 119.42 1.01INTERLOCK Sample 1 962P0H 5.53 75.23 1.15 Sample 1 962P0H 5.83 79.271.17 Sample 2 962P0H 5.81 78.88 1.14 Sample 3 962P0H + 5.64 69.65 0.98GARDIAN Sample 1 962P0H + 7.54 124.48 1.02 INTERLOCK Sample 1 908D1S5.65 76.92 1.23 Sample 1 908D1S 5.69 73.44 1.27 Sample 2 908D1S 5.4870.22 1.16 Sample 3 908D1S + 5.74 72.72 1.05 GARDIAN Sample 1 908D1S +7.57 126.58 0.94 INTERLOCK Sample 1 929P6H 5.62 73.82 1.11 Sample 1929P6H 5.88 80.83 1.15 Sample 2 929P6H 5.85 77.96 1.11 Sample 3 929P6H +5.67 73.36 1.05 GARDIAN Sample 1 926Y7O 6.3 91.54 1.05 Sample 5 926Y7O6.53 100.98 1.21 Sample 6 926Y7O 5.66 75.35 1.11 Sample 7 926Y7O + 5.5874.76 1.11 GARDIAN Sample 2

Analysis of the Table 15d results show that the CLARITY prior artcompositions had a smaller median droplet particle size than inventivecompositions 962P0H Samples 1 and 3, 962P0H+INTERLOCK Sample 1, 908D1SSample 1, 908D1S+GARDIAN Sample 1, 908D1S+INTERLOCK Sample 1, 929P6HSamples 1-3, 929P6H+GARDIAN Sample 1, 926Y7O Sample 5 and 926Y7O+GARDIANSample 1 at comparative dicamba concentrations thereby indicating thatthose inventive compositions provide a larger droplet particle size thanthe comparative prior art compositions.

Example 16

The eye irritation potential of an aqueous formulation of the presentinvention was evaluated. A formulation consisting 61 wt % a.e. aqueousMEA dicamba solution having a pH of 8.5 was prepared. Eye irritationtesting was done according to the methods provided in U.S. EnvironmentalProtection Agency Office of Prevention, Pesticides and Toxic Substances,Health Effects Test Guidelines: OPPTS 870.2400 Acute Eye Irritation. Theeyes of 3 rabbit animals were treated with the formulation and werescored for effects on the cornea, iris, and conjunctivae (redness,swelling and discharge). A FIFRA category 3 rating, or moderatelyirritating, was assigned to the formulation. The results are presentingin Tables 16a-c below.

TABLE 16a Animal 1 Hours Days 2 24 48 72 4 7 10 Cornea Opacity 1 2 1 1 10 0 Area 2 4 4 3 3 4 4 Iris Values 1 1 1 1 1 0 0 Conjunctivae Redness 33 3 3 3 0 0 Chemosis 3 2 2 2 2 0 0 Discharge 3 3 2 1 1 1 0

TABLE 16b Animal 2 Hours Days 2 24 48 72 4 7 10 Cornea Opacity 1 1 1 1 10 0 Area 2 3 3 1 1 4 4 Iris Values 1 1 1 1 0 0 0 Conjunctivae Redness 33 3 2 2 0 0 Chemosis 3 2 2 2 2 0 0 Discharge 3 3 1 0 1 1 0

TABLE 16c Animal 3 Hours Days 2 24 48 72 4 7 10 Cornea Opacity 1 1 1 0 00 0 Area 2 4 4 4 4 4 4 Iris Values 1 1 1 1 1 0 0 Conjunctivae Redness 33 3 2 2 1 3 Chemosis 3 2 2 2 2 0 3 Discharge 3 3 1 1 1 1 3

All treated eyes exhibited corneal opacity, iritis and conjunctivitiswithin 24 hours after treatment. All eyes were free of positive scores 7days after treatment and all irritation by 10 days (conjunctival scoresof 1 are not considered as positive scores). Based on the results of thestudy, the MEA dicamba formulation is considered to be moderatelyirritating to the eye and would likely be classified in FIFRA CategoryIII.

Example 17

The eye irritation potential of formulations 908D1S and 929P6H wereevaluated. Eye irritation testing was conducted to comply with GoodLaboratory Practices (GLP) regulations as defined in: 40 CFR 160 (U.S.EPA GLP Standards-Pesticide Programs (FIFRA) 1989; OECD Principles ofGLP (as revised in 1977) published in ENV/MC/CHEM (98)17, OECD, Paris(1978); and EC Directive 2004/10/EC, Official Journal of the EuropeanUnion, L50/44 (2004). Testing was done according to the protocolprovided in: U.S. Environmental Protection Agency Office of Prevention,Pesticides and Toxic Substances, Health Effects Test Guidelines (OPPTS870.2400) Acute Eye Irritation; OECD Guideline for the Testing ofChemicals, Test No. 405; and Official Journal of the EuropeanCommunities, Methods for the Determination of Toxicity, Part B.5 (EyeIrritation), Directive 2004/73/EC.

The eyes of 3 rabbit animals were treated with each formulation todetermine the potential for formulations 908D1S and 929P6H to produceirritation from a single instillation via the ocular route. Prior totesting of the formulations, one drop of 2% ophthalmic fluoresceinsodium was instilled into both eyes of each rabbit. After about 30seconds, the eyes were rinsed with physiological saline (0.9% NaCl) andthen evaluated and scored for corneal damage and abnormalities using anultraviolet light source. Three healthy rabbits, not previously testedand without preexisting ocular irritation, were selected for testing.Prior to testing of the formulations, 2-3 drops of ocular anesthetic(Tetracaine Hydrochloride Ophthalmic Solution 0.5%) were placed in eachof both eyes of each rabbit. One tenth of a milliliter of the evaluatedformulation was instilled in the right eye of the rabbit. The left eyeremained untreated and served as a control. Ocular irritation wasevaluated at 1, 24, 48 and 72 hours by the method of Draize et al.(Methods for the study of irritation and toxicity of substances appliedtopically to the skin and mucous membranes, J. Pharmacol. Exp. Ther.,82:377-390 (1944)). The fluorscein dye evaluation method described abovewas performed at 24 and/or at 48 hours to evaluate the extent of cornealdamage. The time interval with the highest mean score (Maximum MeanTotal Score—MMTS) for all rabbits was used to classify the testsubstance by the system of Kay and Calandra (Kay, J. H. and Calandra, J.C., Interpretation of eye irritation tests, J. Soc. Cos. Chem.,13:281-289 (1962)). The results for formulation 929P6H are presented inTables 17a and b below and the results for formulation 908D1S arepresented in Tables 17c-e below.

TABLE 17a EEC Mean Scores for formulation 929P6H. Corneal IrisConjunctival Conjunctival Rabbit No. Opacity Lesion Redness Chemosis 1(Male) 0.3 0.0 1.0 0.0 2(Female) 0.0 0.0 0.0 0.0 3(Female) 0.0 0.0 0.00.0

Formulation 929P6H is classified as mildly irritating to the eye andmeets the requirements for the EC classification of “No classificationfor ocular irritation.

TABLE 17b Individual scores for ocular irritation for formulation 929P6HHour 1 Hour 24 Hour 48 Hour 72 Rabbit No. 1 (Male) I. Cornea A. Opacity0  1^(a)  0^(a) 0 B. Area 4 1 4 4 (A × B) × 5 0 5 0 0 II. Iris A. Values0 0 0 0 A × 5 0 0 0 0 III. Conjunctivae A. Redness 2 2 1 0 B. Chemosis 10 0 0 C. Discharge 2 2 1 0 (A + B + C) × 2 10 8 4 0 Total 10 13  4 0Rabbit No. 2 (Female) I. Cornea A. Opacity 0  0^(a) 0 0 B. Area 4 4 4 4(A × B) × 5 0 0 0 0 II. Iris A. Values 0 0 0 0 A × 5 0 0 0 0 III.Conjunctivae A. Redness 1 0 0 0 B. Chemosis 0 0 0 0 C. Discharge 2 0 0 0(A + B + C) × 2 6 0 0 0 Total 6 0 0 0 Rabbit No. 3 (Female) I. Cornea A.Opacity 0  0^(a) 0 0 B. Area 4 4 4 4 (A × B) × 5 0 0 0 0 II. Iris A.Values 0 0 0 0 A × 5 0 0 0 0 III. Conjunctivae A. Redness 2 0 0 0 B.Chemosis 1 0 0 0 C. Discharge 2 1 0 0 (A + B + C) × 2 10 2 0 0 Total 102 0 0 ^(a)2% ophthalmic fluorscein used to evaluate the extent or verifythe absence of corneal opacity

TABLE 17c EEC Mean Scores for formulation 908D1S Corneal IrisConjunctival Conjunctival Rabbit No. Opacity Lesion Redness Chemosis 4(Female) 1.0 0.0 2.0 1.3 5 (Female) 1.0 0.0 2.0 1.3 6 (Female) 1.0 0.02.0 1.3

Formulation 908D1S is classified as mildly irritating to the eye andmeets the requirements for the EC classification of “No classificationfor ocular irritation.”

TABLE 17d Average scores for ocular irritation for formulation 908D1STime Post Incidence of Positive Effects Instillation Corneal OpacityIritis Conjunctivitis  1 hour 2/3 2/3 3/3 24 hours 3/3 0/3 3/3 48 hours3/3 0/3 3/3 72 hours 3/3 0/3 3/3 Day 4 3/3 0/3 1/3 Day 7 3/3 0/3 0/3 Day10 3/3 0/3 0/3 Day 14 3/3 0/3 0/3 Day 17 3/3 0/3 0/3 Day 21 3/3 0/3 0/3

TABLE 17e Mean scores for severity of irritation for formulation 908D1STime Post Instillation Severity of Irritation (Mean Score)  1 hour 25.024 hours 30.3 48 hours 23.3 72 hours 23.3 Day 4 20.3 Day 7 19.7 Day 1017.3 Day 14 15.3 Day 17 16.0 Day 21 11.0

One hour after instillation of formulation 908D1S, two of the threetreated eyes exhibited corneal opacity and iritis, and “positive”conjunctivitis was evident in all three eyes. By 24-hours iritis hadcleared from both affected eyes, however, corneal opacity andconjunctivitis were present in all three treated eyes. The overallincidence and severity of irritation decreased gradually thereafter.Pannus was observed in all three eyes between Days 14 and 21. By studytermination (Day 21), corneal opacity persisted in all treated eyes withminimal conjunctivitis noted in two eyes.

When introducing elements of the present invention or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

In view of the above, it will be seen that the several objects of theinvention are achieved and other advantageous results attained.

As various changes could be made in the above methods, formulations andprocesses without departing from the scope of the invention, it isintended that all matter contained in the above description and shown inthe accompanying drawing shall be interpreted as illustrative and not ina limiting sense.

1-166. (canceled)
 167. A method for reducing the volatility of an auxinherbicide from a herbicidal application mixture, the method comprising:mixing (a) an auxin herbicide salt selected from the group consisting ofagriculturally acceptable salts of 2,4-D, 2,4-DB, dichlorprop, MCPA,MCPB, aminopyralid, clopyralid, fluroxypyr, triclopyr, mecoprop,mecoprop-P, dicamba, picloram, quinclorac, aminocyclopyrachlor, racemicmixtures thereof, resolved isomers thereof, and mixtures thereof, (b) asalt of glyphosate, and (c) water to form the herbicidal applicationmixture, wherein the amount of auxin herbicide salt that is mixed issuch that the herbicidal application mixture has an auxin herbicideconcentration from about 0.1 to about 50 g a.e./L, and mixing a base orpH buffer with the application mixture such that the base or pH bufferraises the pH of the herbicidal application mixture to be within therange from about 5 to about 10 and the base or pH buffer comprises anion selected from the group consisting of sodium, potassium,dimethylammonium, monoethanolammonium, isopropylammonium,diglycolammonium, and mixtures thereof.
 168. The method of claim 167wherein the auxin herbicide comprises an agriculturally acceptable saltof dicamba.
 169. The method of claim 168 wherein the auxin herbicidecomprises at least one salt of dicamba selected from the groupconsisting of the sodium salt of dicamba, potassium salt of dicamba,monoethanolamine salt of dicamba, diglycolamine salt of dicamba, andmixtures thereof.
 170. The method of claim 167 wherein the pH of theherbicidal application mixture is from about 7 to about
 9. 171. Themethod of claim 167 wherein the base or pH buffer comprises a sodium orpotassium ion.
 172. The method of claim 167 wherein the method furthercomprises mixing one or more soluble polybasic polymers with theherbicidal application mixture.
 173. The method of claim 167 wherein theweight ratio on an acid equivalent basis of the auxin herbicide salt tothe salt of glyphosate in the herbicidal application mixture is fromabout 5:1 to about 1:5.
 174. The method of claim 167 wherein the weightratio on an acid equivalent basis of the auxin herbicide salt to thesalt of glyphosate in the herbicidal application mixture is from about3:1 to about 1:3.
 175. The method of claim 168 wherein the salt ofdicamba comprises the diglycolamine salt of dicamba and the weight ratioon an acid equivalent basis of the auxin herbicide to glyphosate in theherbicidal application mixture is from about 3:1 to about 1:3.
 176. Themethod of claim 168 wherein the salt of dicamba comprises themonoethanolamine salt of dicamba and the weight ratio on an acidequivalent basis of the auxin herbicide to glyphosate in the herbicidalapplication mixture is from about 3:1 to about 1:3.
 177. The method ofclaim 167 further comprising applying the herbicidal application mixtureto a weed.
 178. A method for reducing the volatility of dicamba from aherbicidal application mixture, the method comprising: mixing a salt ofdicamba, a salt of glyphosate, and water, to form the herbicidalapplication mixture, wherein the amount of dicamba salt that is mixed issuch that the herbicidal application mixture has a dicamba saltconcentration from about 0.1 to about 50 g a.e./L, and the weight ratioon an acid equivalent basis of the salt of dicamba to the salt ofglyphosate in the herbicidal application mixture is from about 50:1 toabout 1:5, and mixing a base or pH buffer with the application mixtureto increase the pH of the application mixture to from about 5 to about10, wherein the base or pH buffer comprises an ion selected from thegroup consisting of sodium, potassium, dimethylammonium,monoethanolammonium, isopropylammonium, diglycolammonium, and mixturesthereof.
 179. The method of claim 178 wherein the salt of dicambacomprises at least one salt of dicamba selected from the groupconsisting of the sodium salt of dicamba, potassium salt of dicamba,monoethanolamine salt of dicamba, diglycolamine salt of dicamba, andmixtures thereof.
 180. The method of claim 178 wherein the pH of theherbicidal application mixture is from about 7 to about
 9. 181. Themethod of claim 178 wherein the method further comprises mixing one ormore soluble polybasic polymers with the herbicidal application mixture.182. The method of claim 178 wherein the weight ratio on an acidequivalent basis of the salt of dicamba to the salt of glyphosate in theherbicidal application mixture is from about 5:1 to about 1:5.
 183. Themethod of claim 182 wherein the weight ratio on an acid equivalent basisof the salt of dicamba to the salt of glyphosate in the herbicidalapplication mixture is from about 3:1 to about 1:3.
 184. The method ofclaim 178 further comprising applying the herbicidal application mixtureto a weed.